IR cut filter, method for manufacturing the same, and solid-state imaging device

ABSTRACT

A solid-state imaging device comprises a CMOS sensor, a circuit board, a ceramic plate, an IR cut filter, a taking lens, a lens holder, and a support barrel. The CMOS sensor is mounted on the circuit board. The circuit board is fixed to the ceramic plate such that the CMOS sensor is placed inside an opening of the ceramic plate. The sides of the CMOS sensor are surrounded by the ceramic plate. The IR cut filter is fixed to the ceramic plate so as to cover the opening. The CMOS sensor is disposed behind the taking lens. The IR cut filter is disposed between the taking lens and the CMOS sensor. A light-shielding layer is formed over the entire periphery of edge portions of an incident surface of the IR cut filter. Harmful rays such as reflective light is blocked by the light-shielding layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2013/081908 filed on Nov. 27, 2013, which claims priority under 35U. S. C. § 119 (a) to Japanese Patent Application No. 2012-264798, filedDec. 3, 2012. Each of the above application(s) is hereby expresslyincorporated by reference, in its entirety, into the presentapplication.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an IR cut filter that cuts IR lighttraveling toward a solid-state imaging element, a method formanufacturing an IR cut filter, and a solid-state imaging device.

2. Description Related to the Prior Art

A solid-state imaging device comprises a taking lens, a solid-stateimaging element disposed behind the taking lens, a circuit board onwhich the solid-state imaging element is mounted. The solid-stateimaging device is incorporated in an electronic device such as a digitalcamera, a mobile phone with a camera, a smartphone, or the like. Thesolid-state imaging element is an image sensor of a CCD-type, a CMOStype, or the like. The solid-state imaging element photoelectricallyconverts light incident on a light receiving surface to output threecolor signals. The three color signals are subjected to signalprocessing in a signal processing circuit incorporated in the electronicdevice, and then converted into image data. A taken image is displayedon a monitor based on the image data.

The sensitivity of the solid-state imaging element to the near-infraredregion is higher than that of a human eye. In the case where the wholelight including the IR (infrared) light is incident on the solid-stateimaging element and photoelectrically converted, an image of a subjectseen with human eyes and a taken image differ in color balance. Forexample, a green object appears as a gray or a reddish brown object anda blue-violet object appears as a reddish-violet object in the takenimage.

In a solid-state imaging device described in US 2012/0257075 A1(corresponding to JP 2012-222546 A), an IR cut filter, which cuts theinfrared light while transmitting visible light, is provided between ataking lens and a solid-state imaging element to prevent the infraredlight from entering the solid-state imaging element. Thereby, the colorbalance seen with the human eyes is reproduced in a taken image.

In the solid-state imaging device, harmful rays are caused by repetitivereflection and refraction of the visible light. Upon incidence on thesolid-state imaging element, the harmful rays may cause so-called flarethat is light fogging, resulting in degradation of image quality. In theUS 2012/0257075 A1, the IR cut filter cuts the infrared light, but theharmful rays pass through the IR cut filter. The harmful rays areincident on the slid-state imaging element, causing the flare and also aphenomenon called “ghost” which is a clear appearance of the harmfulrays in an image.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an IR cut filter forinhibiting occurrences of flare and ghost, a method for manufacturingthe same, and a solid-state imaging device.

In order to achieve the above object, the IR cut filter of the presentinvention comprises a filter body and a light-shielding layer. The IRcut filter is disposed and used on a light receiving surface side of asolid-state imaging element. The filter body cuts IR light of subjectlight traveling toward the light receiving surface. The light-shieldinglayer is formed over at least one of an edge portion of an incidentsurface of the filter body and a side end face of the filter body, andblocks visible light. The light-shielding layer includes a layer inwhich the size of a polymerizable composition particle is small and alow reflective layer in which the size of the polymerizable compositionparticle is large.

It is preferred that the light-shielding layer is formed over the edgeportion of the incident surface. It is preferred that a length L1 from aside end of the incident surface to a side end of the solid-stateimaging element in an orthogonal direction, which is orthogonal to anoptical axis direction, and a length L2 from a side end of the filterbody to an inner end of the light-shielding layer in the orthogonaldirection satisfy L2≤L1.

It is preferred that the light-shielding layer contains carbon black ortitanium black. It is preferred that the light-shielding layer is formedby a spin coating method or a spray coating method.

It is preferred that the light-shielding layer is formed over the sideend face. It is preferred that a length L3 of the filter body in theoptical axis direction and a length L4 from the incident surface to arear end of the light-shielding layer in the optical axis directionsatisfy L4≤L3. It is preferred that a reflectivity of thelight-shielding layer is 2% or less and surface roughness is 0.55 μm ormore.

The method for manufacturing an IR cut filter according to the presentinvention comprises a coating film forming step, an exposure step, and adevelopment step. The IR cut filter is disposed and used on a lightreceiving surface side of a solid-state imaging element. In the coatingfilm forming step, a coating liquid for forming a light-shielding layeris applied by a spin coating method or spray coating method to at leastone of an incident surface and a side end surface of a filter body toform a coating film. The light-shielding layer blocking visible light.The filter body cuts IR light of subject light traveling toward thelight receiving surface of the solid-state imaging element. The coatingliquid contains a curing component that is cured by irradiation withlight. In the exposure step, the coating film is irradiated with thelight through a mask to cure an irradiated portion of the coating film.The mask covers the coating film such that an edge portion of thecoating film is exposed when viewed in a normal direction of theincident surface. In the development step, the light-shielding layer isformed by eluting an unirradiated portion of the coating film into analkaline aqueous solution. The coating film forming step comprises asubstep for forming a film in which the size of polymerizablecomposition particle is small and a substep for forming a low reflectivefilm in which the size of the polymerizable composition particle islarge. The coating film includes the film in which the size of thepolymerizable composition particle is small and the low reflective film.

It is preferred that an average particle diameter of the polymerizablecomposition particles in the film in which the size of the polymerizablecomposition particle is small is 20 μm or less and an average particlediameter of the polymerizable composition particles in the lowreflective film is 70 μm or less.

The solid-state imaging device according to the present inventioncomprises a taking lens, a solid-state imaging element, an IR cutfilter, and a support plate. The solid-state imaging element is disposedon an exit surface side of the taking lens. The IR cut filter isdisposed between the taking lens and the solid-state imaging element.The IR cut filter has a filter body and a light-shielding layer. Thefilter body cuts IR light of subject light traveling toward a lightreceiving surface of the solid-state imaging element. Thelight-shielding layer blocks visible light. The light-shielding layer isformed over at least one of an edge portion of an incident surface ofthe filter body and a side end face of the filter body. Thelight-shielding layer includes a layer in which the size of apolymerizable composition particle is small and a low reflective layerin which the size of the polymerizable composition particle is large.The support plate supports the IR cut filter.

According to the present invention, the harmful rays are blocked by thelight-shielding layer. Thereby the incidence of the harmful rays ontothe light receiving surface of the solid-state imaging element, which iscovered by the IR cut filter, is inhibited and the occurrences of flareand ghost in taken images are inhibited.

BRIEF DESCRIPTION OF DRAWINGS

The above and other objects and advantages of the present invention willbe more apparent from the following detailed description of thepreferred embodiments when read in connection with the accompanieddrawings, wherein like reference numerals designate like orcorresponding parts throughout the several views, and wherein:

FIG. 1 is a perspective view illustrating a solid-state imaging device;

FIG. 2 is an exploded perspective view of the solid-state imagingdevice;

FIG. 3 is a cross-sectional view of the solid-state imaging device;

FIG. 4 is a cross-sectional view illustrating a CMOS sensor, a circuitboard, a ceramic plate, an IR cut filter, and a light-shielding film;

FIG. 5 is an explanatory view illustrating an IR cut filter according toa first embodiment;

FIG. 6 is an explanatory view illustrating a method for forming apolymerizable composition layer with a spin coating method;

FIG. 7 is a table illustrating experimental results regarding presenceor absence of flare in a taken image and acceptance or rejection ofviewing angles, with varying size of the light-shielding layer;

FIG. 8 is a cross-sectional view illustrating a solid-state imagingdevice according to a second embodiment;

FIG. 9 is an explanatory view illustrating a method for manufacturing anIR cut filter in a second embodiment;

FIG. 10 is a cross-sectional view illustrating a CMOS sensor, a circuitboard, a ceramic plate, an IR cut filter, and a light-shielding layeraccording to a second embodiment;

FIG. 11 is a table illustrating experimental results regarding thepresence or absence of flare in a taken image and the acceptance orrejection of viewing angles in a case where the size of thelight-shielding layer is varied in the solid-state imaging device of thesecond embodiment;

FIG. 12 is a cross-sectional view of a solid-state imaging deviceaccording to a third embodiment;

FIG. 13 is an explanatory view of a method for manufacturing an IR cutfilter according to the third embodiment; and

FIG. 14 is a cross-sectional view illustrating a solid-state imagingdevice according to a fourth embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[First Embodiment]

As illustrated in FIG. 1 and FIG. 2, a solid-state imaging device 2comprises an image sensor 3, being a solid-state imaging element, acircuit board 4 on which the image sensor 3 is mounted, and a ceramicplate 5 to which the circuit board 4 is attached. The solid-stateimaging device 2 comprises an IR cut filter 10, a taking lens 7, a lensholder 8, and a support barrel 9. The IR cut filter 10 is attached tothe ceramic plate 5 and cuts infrared light (IR). The ceramic plate 5 isa support plate for supporting the IR cut filter 10. The lens holder 8holds the taking lens 7. The support barrel 9 holds the lens holder 8 ina movable manner. Note that the number of the taking lens 7 may bechanged as necessary. The image sensor 3 in this embodiment is of a CMOStype. The image sensor 3 may be of a CCD type instead. The solid-stateimaging device 2 is incorporated in an electronic device, for example, adigital camera. Hereinafter, an example in which the solid-state imagingdevice 2 is incorporated in a digital camera is described.

The image sensor 3 is mounted at the center of one of surfaces of thecircuit board 4. The ceramic plate 5 has the shape of a frame formedwith an opening 5 a. The image sensor 3 is disposed within the opening 5a. The circuit board 4 is fixed to the ceramic plate 5 such that theceramic plate 5 surrounds the sides of the image sensor 3. The circuitboard 4 and the ceramic plate 5 are fixed to each other with an adhesive(for example, an epoxy-based adhesive, the same hereinafter). Variouscircuit patterns are formed in the circuit board 4.

The IR cut filter 10 has a filter body 6 and a light-shielding layer 11,which will be described below. The filter body 6 cuts the IR light, andhas plate-shaped glass formed with a reflective film (not shown) thatreflects the IR light. The surface of the reflective film is an incidentsurface 6 a on which subject light is incident. The filter body 6 isformed with the size slightly greater than that of the opening 5 a, andfixed to the ceramic plate 5 with the adhesive so as to cover theopening 5 a.

The taking lens 7 is formed with the diameter greater than that of thefilter body 6. The lens holder 8 is formed with an opening at itscenter, and the taking lens 7 is mounted inside the opening. The supportbarrel 9 is fixed using the adhesive to the surface of the ceramic plate5 on the IR cut filter 10 side. The support barrel 9 holds the lensholder 8 inside the support barrel 9 such that the lens holder 8 ismovable in an optical axis direction (an up-and-down direction in FIG.3). The lens holder 8 is moved inside the support barrel 9 in theoptical axis direction by a moving mechanism (not shown).

In the solid-state imaging device 2 thus configured, the image sensor 3is disposed on an exit surface side (the exit side) (in a lower portionin FIG. 2 and FIG. 3) of the taking lens 7. The IR cut filter 10 isdisposed between the taking lens 7 and the image sensor 3. The subjectlight is incident on a light receiving surface of the image sensor 3through the taking lens 7 and the IR cut filter 10. The infrared lightcontained in the subject light is cut by the filter body 6.

The circuit board 4 is connected to a control unit incorporated in thedigital camera and power is supplied from a power source (battery) ofthe digital camera to the circuit board 4. A plurality of color pixelsare arranged in two dimensions in the light receiving surface of theimage sensor 3. Each color pixel photoelectrically converts the incidentlight and stores a signal charge generated. The control unit of thedigital camera sequentially reads out the signal charge of each colorpixel from the image sensor 3 and thereby allows outputting an imagesignal of one frame, and performs various types of signal processing onthe image signal of one frame. Thus, a taken image is obtained.

As illustrated in FIG. 2 and FIG. 3, the light-shielding layer 11, whichblocks visible light, is formed over the entire periphery of edgeportions of the incident surface 6 a of the filter body 6. Thelight-shielding layer 11 is formed into a film form. The light-shieldinglayer 11 and the incident surface 6 a with no light-shielding layer 11constitute a colored pattern. In a case where an IR cut filter with nolight-shielding layer 11 is used, the incidence of the reflective light(visible light) R1, which exited from the taking lens 7 and reflected bythe front surface (the top surface in FIGS. 2 and 3) of the ceramicplate 5 and then repeated the reflection and refraction inside the solidstate imaging device, on the image sensor 3 and the incidence of thereflective light (visible light) R2, which exited from the taking lens 7and reflected by the inner wall of the lens holder 8, on the imagesensor 3 cause flare and ghost in a taken image. Since the IR cut filter10 is formed with the light-shielding layer 11, the light-shieldinglayer 11 blocks the harmful rays such as the reflective light R1 and R2traveling toward the image sensor 3. As a result, the flare and ghostare inhibited in a taken image. Note that the thickness of thelight-shielding layer 11 is exaggerated in FIG. 2 and FIG. 3. Asillustrated in FIG. 4, it is preferred to satisfy L2≤L1 where L1 denotesa length from a side end of the filter body 6 to a side end of the imagesensor 3 and L2 denotes a length from the side end of the filter body 6to an inner end of the light-shielding layer 11. Thereby the viewingangle in the case of L2≤L1 is greater than that in the case of L2>L1.

Hereinafter, each component contained in dispersion composition andpolymerizable composition, which are used for forming thelight-shielding layer 11, will be described below in detail.

Note that, in this specification, in a case a group (atomic group) isdenoted without specifying whether it is substituted or unsubstituted,it includes a group having a substituent and a group having nosubstituent. For example, an “alkyl group” includes not only an alkylgroup (unsubstituted alkyl group) having no substituent but also analkyl group (substituted alkyl group) having a substituent.

The “radiation” in this specification includes visible light,ultraviolet rays, far ultraviolet rays, electron beams, X-rays and thelike.

Description of the configuration requirements described below may bemade on the basis of representative embodiments of the presentinvention, but the present invention is not limited to such embodiments.Note that the numerical range expressed by using the word “to” in thisspecification represents a range including the numerical value beforethe word “to” as the lower limit and the numerical value after the word“to” as the upper limit.

Note that, in this specification, “(meth) acrylate” represents anacrylate and methacrylate, “(meth) acrylic” represents acrylic andmethacrylic, “(meth) acryloyl” represents acryloyl and methacryloyl. Amonomer in the present invention is distinguished from an oligomer and apolymer and refers to a compound having the mass average molecularweight of less than or equal to 2,000. In this specification, apolymerizable compound refers to a compound having a polymerizablegroup, and may be a monomer or a polymer. The polymerizable group refersto a group involved in a polymerization reaction.

The dispersion composition for forming the light-shielding layer 11contains (A) a black colorant (preferably titanium black or carbonblack), (B) a dispersant (for example, a polymer compound having astructural unit having a graft chain and a hydrophobic structural unitwhich differs from the structural unit having the graft chain), and (C)a solvent. With the use of this dispersion composition, the dispersioncomposition with high dispersibility, high storage stability, and highcoating properties is obtained.

The polymerizable composition for forming the light-shielding layer 11also contains the above-described dispersion composition, (D) apolymerizable compound, and (E) a polymerization initiator. With the useof this polymerizable composition, a pattern in which a residue in anunexposed portion is inhibited is formed in a case where a patternformation is performed by an exposure process described below. Also, thedevelopment margin and the development latitude in the pattern formationare improved. Here, the high development margin means that the exposedportion is likely to remain at the time of the pattern formation becauseit is difficult to peel off the exposed portion with a developer, andhence a desired pattern is likely to be obtained. The high developmentlatitude means that the duration of time before the formed pattern ispeeled off by the developer is long.

<(A) Black Colorant>

Various types of known black pigments and black dyes may be used asblack colorants. More specifically, carbon black, titanium black,titanium oxide, iron oxide, manganese oxide, graphite, and the like arepreferred from the viewpoint of achieving high optical density with asmall amount. Of those, in particular, at least one of the carbon blackand the titanium black is preferably contained. Especially, the titaniumblack is preferred.

Carbon black disclosed in paragraphs [0020] to [0024] in Japanese PatentUnexamined Application Publication No. 2006-301101 may be used as theabove-mentioned carbon black.

The above-mentioned titanium black is black particles having titaniumatoms, preferably lower titanium oxide, titanium oxynitride, or thelike. The surfaces of titanium black particles may be modified asnecessary for the purpose of improving dispersibility or inhibitingaggregation, and may be coated with silicon oxide, titanium oxide,germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, orthe like. It is also possible to process the surfaces with awater-repellent substance such as those described in Japanese PatentUnexamined Application Publication No. 2007-302836.

Methods for manufacturing the titanium black are as follows: a method inwhich a mixture of titanium dioxide and metallic titanium is heated in areducing atmosphere and reduced (Japanese Patent Unexamined ApplicationPublication No. 49-5432), a method in which ultrafine titanium dioxideobtained by high temperature hydrolysis of titanium tetrachloride isreduced in a reducing atmosphere containing hydrogen (Japanese PatentUnexamined Application Publication No. 57-205322), a method in whichtitanium dioxide or titanium hydroxide is reduced in high temperature inthe presence of ammonia (Japanese Patent Unexamined ApplicationPublication Nos. 60-65069 and 61-201610), a method in which a vanadiumcompound is deposited to titanium dioxide or titanium hydroxide andhigh-temperature reduction is performed in the presence of ammonia(Japanese Patent Unexamined Application Publication No. 61-201610), butthe methods are not limited thereto.

Typically, the titanium black is titanium black particles. It ispreferred that the primary particle diameter of each particle and theaverage primary particle diameter are small. To be more specific, theaverage primary particle diameter is preferably in the range of 10 nm to45 nm, more preferably in the range of 12 nm to 20 nm. Note that theparticle diameter (size) in the present invention, that is, the particlediameter refers to the diameter of a circle having an area equal to theprojected area of the outer surface of the particle. The projected areaof the particle is obtained by measuring the area of the particle takenin an electron micrograph and correcting the magnification. The specificsurface area of the titanium black is not particularly limited.Normally, a value measured by BET (Brunauer, Emmet and Teller's) methodis preferably in the order of 5 m²/g to 150 m²/g, and particularlypreferably 20 m²/g to 100 m²/g so that the water repellency of thetitanium black after the surface treatment using the water-repellentagent exhibits a predetermined performance.

Examples of commercially available titanium black include titanium black10S, 12S, 13R, 13M, 13M-C, 13R, 13R—N, 13M-T (trade name, manufacturedby Mitsubishi Materials Corporation), Tilack D (trade name, manufacturedby Akokasei Co., Ltd.), and the like.

The surfaces of the titanium black particles may be modified asnecessary for the purpose of improving dispersibility, inhibitingaggregation, or the like. As for the modification of the particlesurfaces, for example, silicon oxide, titanium oxide, germanium oxide,aluminum oxide, magnesium oxide, zirconium oxide, or the like may beused for coating treatments. Treatments using the water-repellentsubstances described in the Japanese Patent Unexamined ApplicationPublication No. 2007-302836 may be performed.

Furthermore, it is preferred that the dispersion composition containsthe titanium black as a dispersoid containing the titanium black and Siatoms. In this form, it is preferred that the titanium black iscontained as the dispersoid in the dispersion composition, and a contentratio (Si/Ti) of the Si atoms and Ti atoms in the dispersoid is greaterthan or equal to 0.05 in terms of mass. Here, the above-mentioneddispersoid includes both the titanium black in a state of primaryparticles and the titanium black in a state of aggregates (secondaryparticles). Note that it is preferred that the upper limit of thecontent ratio (Si/Ti) of the Si atoms and the Ti atoms in the dispersoidis 0.5 because it tends to be difficult to manufacture a pigmentdispersion with the dispersoid in case where the content ratio exceeds0.5.

In a case where the Si/Ti of the dispersoid is too small, a residuetends to remain in a removal section from which a polymerizablecomposition layer is removed after the polymerizable composition layer,which will be described below, with the dispersoid is patterned byphotolithography or the like. In a case where the Si/Ti of thedispersoid is too large, the light-shielding ability tends to decrease.For these reasons, the Si/Ti of the dispersoid is preferably 0.05 to 0.5and more preferably 0.07 to 0.4.

To change the Si/Ti of the dispersoid (for example, to 0.05 or more),the following means may be used. First, a dispersion is obtained bydispersing titanium oxide and silica particles with a dispersing machineand then the dispersion is subjected to a reducing process at hightemperature (for example, 850 to 1000° C.). Thereby the dispersoidmostly composed of the titanium black particles and containing the Siand the Ti is obtained.

Here, specific examples for changing the Si/Ti in the dispersoid aredescribed. The titanium black with the Si/Ti adjusted to, for example,0.05 or more is prepared by methods described in, for example,paragraphs [0005] (6) and [0016] to [0021] in Japanese Patent Laid-OpenPublication No. 2008-266045.

In the present invention, the content ratio (Si/Ti) between the Si atomsand the Ti atoms in the dispersoid containing the titanium black and theSi atoms is adjusted to a suitable range (for example, 0.05 or more).Thereby, in the case where the light-shielding layer 11 is formed fromthe composition containing such dispersoid, an amount of the residue,which is derived from the polymerizable composition, remaining on theoutside of a region where the light-shielding layer 11 is formed isreduced. Note that the residue contains a component derived from thetitanium black particles or photosensitive polymerizable compositionsuch as a resin component.

The reason why the residue decreases has not been clarified yet. Theabove-mentioned dispersoid tends to have small particle diameter (e.g.the particle diameter of 30 nm or less). The adsorption to theunderlying film of the whole light-shielding layer 11 is reduced as thecomponent containing the Si atoms increases in the dispersoid. This isassumed to contribute to improvement of the development removability ofuncured polymerizable composition (particularly, the titanium blackparticles) in the formation of the light-shielding layer 11.

Since the titanium black is excellent in light-shielding properties tolight in a wavelength region over a wide range from ultraviolet toinfrared, the light-shielding layer 11 formed from the dispersoidcontaining the titanium black and the Si atoms (preferably with theSi/Ti of 0.05 or more in terms of mass) exhibits excellentlight-shielding properties.

Note that the content ratio (Si/Ti) of the Si atoms and the Ti atoms inthe dispersoid is measured by using a method (1-1) or a method (1-2)described below.

<Method (1-1)>

A titanium black dispersion or a polymerizable composition containing atitanium black dispersion liquid and a polymerizable compound was heatedin an oxygen atmosphere, and the dispersoid containing the titaniumblack, being the black colorant (A), and the Si atoms was taken out.

20 mg of the titanium black dispersion or the polymerizable compositionwas weighed, and 0.1 mL of HF, 1 mL of HNO₃ (10% aq.), 1 mL of H₂SO₄ (5%aq.), and 1 mL of HCL (3% aq.) were added thereto, and then this liquiddispersion is subjected to microwave dissolution. At this time, theliquid temperature was 180° C. Note that “aq.” denotes aqueous solution.

Thereafter, H₂O was added to the liquid dispersion until it reaches 100ml, and then the liquid dispersion was subjected to ICP-OES (trade name:Attom, manufactured by SII Co.) for performing elemental analysis. Fromthe results obtained, the mass ratio of Si/Ti is calculated.

<Method (1-2)>

Titanium black dispersion, or a polymerizable composition containing apolymerizable compound and the titanium black dispersion was heated to700° C. in an oxygen atmosphere with a small rotary kiln (a product ofMotoyama, Ltd.) and the temperature was maintained for 30 minutes, andthen cooled. Thereby 2 g of powder was obtained. The obtained powder isplaced on a tungsten plate with the thickness of 0.2 mm. The tungstenplate is set in a vacuum chamber equipped with an electron beam heatingmechanism. The degree of vacuum is 10⁻⁵ Torr or less. The heat treatmentwas performed by electron beam heating for 30 seconds at 1000° C. Basedon the powder subjected to the heat treatment, the Si atomic weight andthe Ti atomic weight were obtained using field emission scanningelectron microscope S-4800 (trade name, manufactured by HitachiTechnologies) and energy dispersive X-ray fluorescence detector INCAEnergy PentaFETx3 (trade name, manufactured by Oxford Co.), to calculatethe Si/Ti ratio.

As for the dispersoid contained in the cured film (the polymerizablecomposition layer) that is obtained by curing the polymerizablecomposition, a method (2) described below is used to determine whetherthe content ratio (Si/Ti) between the Si atoms and the Ti atoms in thedispersoid is 0.05 or more.

<Method (2)>

A cross-section of the polymerization composition layer is formed bydividing the substrate on which the polymerization composition layer isformed. The Si atomic weight and the Ti atomic weight in the surface ofthe polymerizable composition layer with respect to the cross-sectionare obtained using an energy dispersive X-ray fluorescence analyzer. Aratio between these quantities is evaluated as Si/Ti in thepolymerizable composition layer. As for the energy dispersive X-rayfluorescence analysis in this case, S-4800 (trade name) manufactured byHitachi High-Technologies Co., Ltd. is used as the scanning electronmicroscope and INCA Energy PentaFETx3 (trade name) manufactured byOxford Inc. is used as an energy dispersive X-ray fluorescence detectoras with the above.

In the dispersoid containing the titanium black and the Si atoms, theabove-mentioned titanium black can be used. Further, in the dispersoid,one or two or more types of composite oxides such as Cu, Fe, Mn, V, andNi, cobalt oxide, iron oxide, a black pigment composed of carbon black,aniline black, or the like may be combined with the titanium black asthe dispersoid, for the purpose of adjusting dispersibility, colorationproperties, and the like. In this case, it is preferred that thedispersoid composed of the titanium black occupies 50 mass % or more ofthe whole dispersoid.

Further, in the dispersoid, another colorant (such as an organic pigmentor dye) may be used together with the black colorant as desired for thepurpose of adjusting light-shielding properties as long as the colorantdoes not impair the effects of the present invention.

The following describes the materials used in introducing the Si atomsin the dispersoid. In order to introduce the Si atoms in the dispersoid,an Si-containing material such as silica may be used. The silica used inthe present invention may be precipitated silica, fumed silica,colloidal silica, synthetic silica, or the like and is selected asappropriate. The silica is also commercially available. Examples of thesilica particles include HS-101, HS-102, HS-103, HS-104, HS-105, HS-106,HS-107, HS-201, HS-202, HS-203, HS-204, HS-205, HS-301, HS-302, HS-303,HS-304, HS-305 (trade name) manufactured by Nippon Steel Materials Ltd.;Haipureshika SS, Haipureshika TS, Haipureshika BS, Haipureshika SP, andHaipureshika FQ (trade name) manufactured by Ube-Nitto Kasei; CAB-O-SIL(registered trademark) LM-150, CAB-O-SIL (registered trademark) LM-150,and CAB-O-SIL (registered trademark) S-17D manufactured by Cabot.

It is preferred to use fine-particle type silica as the silica particlesbecause the light-shielding properties decrease in the case where theparticle diameter of the silica particles is substantially the same asthe thickness of the light-shielding layer 11. The examples of thefine-particle type silica include, for example, AEROSIL (registeredtrademark) 90, AEROSIL (registered trademark) 130, AEROSIL (registeredtrademark) 150, AEROSIL (registered trademark) 200, AEROSIL (registeredtrademark) 300, AEROSIL (registered trademark) 380, AEROSIL (registeredtrademark) OX 50, AEROSIL (registered trademark) EG 50, AEROSIL(registered trademark) TT 600, AEROSIL (registered trademark) 200 SP,AEROSIL (registered trademark) 300 SP, AEROPERL (registered trademark)300/30, AEROSIL (registered trademark) R 972, AEROSIL (registeredtrademark) R 974, AEROSIL (registered trademark) R 104, AEROSIL(registered trademark) R 106, AEROSIL (registered trademark) R 202,AEROSIL (registered trademark) R805, AEROSIL (registered trademark) R812, AEROSIL (registered trademark) R 812 S, AEROSIL (registeredtrademark) R 816, AEROSIL (registered trademark) R 7200, AEROSIL(registered trademark) R 8200, AEROSIL (registered trademark) R 9200,AEROSIL (registered trademark) MOX 80, AEROSIL (registered trademark)MOX 170, AEROSIL (registered trademark) COK 84, AEROSIL (registeredtrademark) RY 50, AEROSIL (registered trademark) NY 50, AEROSIL(registered trademark) RY 200, AEROSIL (registered trademark) RY 200,AEROSIL (registered trademark) RX 50, AEROSIL (registered trademark) NAX50, AEROSIL (registered trademark) RX 200, AEROSIL (registeredtrademark) RX 300, AEROSIL (registered trademark) R 504, AEROPERL(registered trademark) 300/30, VPAEROPERL (registered trademark) P25/20M05; S6, MA1004 (trade name, the same hereinafter), MA1006, MA1010,MA1013, MX030W, MX050W, MX100W, KE-E30, KE-E40, KE-E50, KE-E70, KE-E150,KE-P10, KE-P30, KE-P50, KE-P100, KE-P150, KE-P250 manufactured bySHOKUBAI KASEI Co.; HS-101 (trade name, the same hereinafter), HS-102,HS-103, HS-104, HS-105, HS-106, HS-107, HS-201, HS-202, HS-203, HS-204,HS-205, HS-301, HS-302, HS-303, HS-304, and HS-305 manufactured byNippon Steel Materials; Haipureshika SS (trade name, the samehereinafter), Haipureshika TS, Haipureshika BS, Haipureshika SP, andHaipureshika FQ manufactured by Ube-Nitto Kasei Co., Ltd.; CAB-O-SIL(registered trademark, the same hereinafter) LM-150, CAB-O-SIL LM-150,and CAB-O-SIL S-17D manufactured by Cabot, but are not limited thereto.

The dispersion composition and the polymerizable composition may containonly one type of titanium black or two or more types of titanium black.

The content of the titanium black, with respect to the total solidcontent of the dispersion composition, is preferably in a range of 20mass % to 94 mass %, more preferably in a range of 40 mass % to 92 mass%, and still more preferably in a range of 40 mass % to 80 mass %.

The content of the titanium black, with respect to the total solidcontent of the polymerizable composition, is preferably in a range of 5mass % to 80 mass %, more preferably in a range of 10 mass % to 70 mass%, and still more preferably in a range of 20 mass % to 60 mass %. Inthe case where the content of the titanium black is within the aboverange, the curability of the polymerizable composition is excellent anda uniform film is formed.

The light-shielding layer 11 having sufficient light-shieldingproperties is formed with a content of the titanium black in highconcentration.

<(A′) Pigments Other than Titanium Black>

In addition to the titanium black, an extender pigment may be added asnecessary to the dispersion composition or the polymerizable compositionof the present invention. Examples of the extender pigments includebarium sulfate, barium carbonate, calcium carbonate, silica, basicmagnesium carbonate, alumina white, gloss white, titanium white, andhydrotalcite. These extender pigments can be used singly or incombination of two or more. Normally, the amount of the extender pigmentis 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and morepreferably 10 to 40 parts by mass, with respect to 100 parts by mass ofthe titanium black. In the present invention, the surfaces of theabove-mentioned titanium black and extender pigments may be optionallymodified with a polymer.

In the dispersion composition and the polymerizable composition of thepresent invention, a substance other than the titanium black may be usedas a light-shielding pigment. Such light-shielding pigment to bedispersed is not particularly limited as long as it has an absorbance inthe visible range.

Examples of such pigments include the above-mentioned extender pigments,the carbon black, the following organic pigments, and the like.

<Organic Pigments>

An organic pigment described in paragraphs [0031] to [0033] of JapanesePatent Unexamined Application Publication No. 2011-057964 may be used asthe organic pigment of the present invention. A pigment chosen from redorganic pigments, yellow organic pigments, violet organic pigments,orange organic pigments, brown organic pigments, and black organicpigments may be used. Examples of the red organic pigments include C. I.Pigment, Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41,48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1,63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123,144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177,178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210,216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, and 279. Examplesof the violet organic pigments include C. I. Pigment Violet 1, 2, 19,23, 27, 29, 32, 37, and 42.

Examples of the yellow organic pigments include C. I. Pigment Yellow 1,2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34,35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65,73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108,109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127,128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156,161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176,177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, and 214.

Examples of the orange pigments include C. I. Pigment Orange 2, 5, 13,16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62,64, 71, and 73.

Of the organic pigments, preferred are diketopyrrolopyrrole-basedpigments, perylene-based pigments, benzimidazolone-based pigments,perinone-based pigments, naphthol-AS-based pigments, anthraquinone-basedpigments, pyrazolone-based pigments, or isoindolinone-based pigments andmore preferred are the diketopyrrolopyrrole-based pigments, theperylene-based pigments, the naphthol-AS-based pigments, and theanthraquinone-based pigments from the viewpoint of not impairing lighttransmittance in a short wavelength range (especially less than or equalto 400 nm) and of improving the light-shielding properties in thevisible range. In particular, preferred are the C. I. Pigment Red 122,150, 171, 175, 177, 209, 224, 242, 254, 255, 264; the C. I. PigmentYellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;and the C. I. Pigment Orange 36, 38, 43, 64, and 71.

<Pigments Other than Those Described Above>

In addition to the above-described pigments, an organic pigment of adifferent color such as green, blue, or black, or an extender pigmentmay be used as necessary for the purpose of adjusting the lighttransmittance in a light-transmitting region and a light-shieldingregion, or the like. Examples of the organic pigments of differentcolors include C. I. Pigment Green 7, 10, 36, 37, 58; C. I. Pigment Blue1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80; C.I. Pigment Brown 25, 28; and C. I. Pigment Black 1 and 7.

Examples in which a light-shielding pigment other than the titaniumblack is mixed include a mixture of the titanium black and the carbonblack in proportions of 6:1 and a mixture of the titanium black and thetitanium oxide in proportions of 3:1. The light-shielding pigment (otherthan the titanium black) to be mixed is used in a range of 0.01 to 99.99parts by mass with respect to the titanium black of 100 parts by mass,more preferably, in a range of 20 to 70 parts by mass.

<(B) Dispersant>

A dispersant (B) is preferably a dispersant composed of polymer compound(B1), more preferably a polymer compound containing a structural unithaving a graft chain and a hydrophobic structural unit different fromthe structural unit having the graft chain.

Examples of the polymer compounds (B1) include polymeric dispersants(for example, polyamidoamine and salts thereof, polycarboxylic acids andsalts thereof, high molecular weight unsaturated acid ester, modifiedpolyurethane, modified polyester, modified poly (meth) acrylates, (meth)acrylic copolymers, and naphthalenesulfonic acid-formaldehydecondensate), polyoxyethylene alkyl phosphoric acid esters,polyoxyethylene alkyl amines, alkanolamines, and pigment derivatives.

The polymer compounds (B1) are further classified into linear polymers,terminal-modified polymers, graft polymers, and block polymers based onthe structure.

The polymer compound (B1) is held by adsorption on the surfaces of thedispersoid such as the titanium black particles and the pigmentoptionally used in combination with the titanium black particles, andacts to prevent reaggregation. Therefore, examples of the preferredstructures thereof include an end-modified polymer having an anchor siteto the pigment surface, a graft polymer, and a block polymer.

On the other hand, by modifying the surfaces of the dispersoid includingthe titanium black particles or the above-mentioned titanium black andthe Si atoms, the adsorption properties of the polymer compound (B1) tothe dispersoid may be enhanced.

The polymer compound (B1) has a structural unit having a graft chain asdescribed above. Note that in this specification, the term “structuralunit” is synonymous with the term “repeat unit”. Such polymer compound(B1) having a structural unit having a graft chain has an affinity for asolvent due to the graft chain, so that the polymer compound (B1) isexcellent in dispersibility of the titanium black particles anddispersion stability with time. Owing to the presence of a graft chain,the polymerizable composition has an affinity for a polymerizablecompound, resin possibly combined, or the like, so that it is lesslikely that the alkali development causes a residue.

In a case where a graft chain is long, steric repulsion effect is highand dispersibility is improved. However, in a case where the graft chainis too long, the adsorption force to the titanium black is reduced, sothat the dispersibility tends to be lowered. Therefore, the number ofatoms excluding hydrogen atoms in the graft chain is preferably in therange of 40 to 10,000, more preferably in the range of 50 to 2000, andstill more preferably in the range of 60 to 500. Here, the graft chainrefers to a portion from the base (an atom which is in a group branchedfrom the main chain and which is bonded to the main chain) of the mainchain of a copolymer to the end of the group which is branched from themain chain.

It is preferred that the graft chain has a polymer structure. Examplesof the polymer structures include a polyacrylate structure (e.g. a poly(meth) acrylic structure), a polyester structure, a polyurethanestructure, a polyurea structure, a polyamide structure and a polyetherstructure.

In order to improve the interaction of the graft sites and a solvent,and to thereby increase the dispersibility, it is preferred that thegraft chain has at least one structure selected from a group consistingof the polyester structure, the polyether structure, and thepolyacrylate structure. It is more preferred that the graft chain has atleast one of the polyester structure and the polyether structure.

The structure of a macromonomer having such a polymer structure in theform of a graft chain is not particularly limited as long as it has asubstituent capable of reacting with a polymer main chain unit and meetsthe requirements of the present invention. It is preferred to use amacromonomer with a reactive double bond group.

Examples of commercially available macromonomers which correspond to thestructural unit having a graft chain of the polymer compound (B1) andwhich are suitable for use in the synthesis of the polymer compound (B1)include AA-6 (trade name, (trade name, TOAGOSEI Co., Ltd.), AA-10 (tradename, manufactured by TOAGOSEI CO., Ltd.), AB-6 (trade name,manufactured by TOAGOSEI Co., Ltd.), AS-6 (TOAGOSEI Co., Ltd.), AN-6(trade name, manufactured by TOAGOSEI Co., Ltd.), AW-6 (trade name,manufactured by TOAGOSEI Co., Ltd.), AA-714 (trade name, manufactured byTOAGOSEI Co., Ltd.), AY-707 (trade name, manufactured by TOAGOSEI Co.,Ltd.), AY-714 (trade name, manufactured by TOAGOSEI Co., Ltd.), AK-5(trade name, manufactured by TOAGOSEI Co., Ltd.), AK-30 (trade name,manufactured by TOAGOSEI Co., Ltd.), AK-32 (trade name, manufactured byTOAGOSEI Co., Ltd.), BLEMMER PP-100 (trade name, manufactured by NOFCo., Ltd.), BLEMMER PP-500 (trade name, NOF Corporation), BLEMMER PP-800(trade name, manufactured by NOF Co., Ltd.), BLEMMER PP-1000 (tradename, manufactured by NOF Co., Ltd.), BLEMMER 55-PET-800 (manufacturedby NOF Co., Ltd.), BLEMMER PME-4000 (trade name, manufactured by NOFCo., Ltd.), BLEMMER PSE-400 (trade name, manufactured by NOF Co., Ltd.),BLEMMER PSE-1300 (trade name, manufactured by NOF Co., Ltd.), BLEMMER43PAPE-600B (trade name, manufactured by NOF Co., Ltd.), and the like.Of those, the AA-6 (manufactured by TOAGOSEI Co., Ltd.), the AA-10(trade name, TOAGOSEI Co., Ltd.), the AB-6 (trade name, manufactured byTOAGOSEI Co., Ltd.), the AS-6 (trade name, TOAGOSEI Co., Ltd.), the AN-6(trade name, manufactured by TOAGOSEI Co. Ltd.), and BLEMMER PME-4000(trade name, manufactured by NOF Co., Ltd.), are preferably used.

The polymer compound (B1) preferably contains a structural unitrepresented by any one of the following formulas (1) to (4) as thestructural unit having a graft unit, more preferably a structural unitrepresented by any one of the following formulas (1A), (2A), (3A), (3B),and (4).

In the formulas (1) to (4), each of W¹, W², W³, and W⁴ independentlyrepresents an oxygen atom or NH. It is preferred that W¹, W², W³, and W⁴is an oxygen atom.

In the formulas (1) to (4), each of X¹, X², X³, X⁴, and X⁵ independentlyrepresents a hydrogen atom or a monovalent organic group. In terms ofconstraints of synthesis, it is preferred that each of X¹, X², X³, X⁴,and X⁵ independently represents a hydrogen atom or an alkyl group withthe number of carbon atoms from 1 to 12. It is more preferred that eachof X¹, X², X³, X⁴, and X⁵ independently represents a hydrogen atom or amethyl group. The methyl group is particularly preferred.

In the formulas (1) to (4), each of Y¹, Y², Y³, and Y⁴ independentlyrepresents a divalent linking group, and the linking group is notparticularly limited structurally. Specific examples of the divalentlinking groups represented by Y¹, Y², Y³, and Y⁴ include the followinglinking groups represented by (Y-1) to (Y-21). In the structures shownbelow, A and B denote binding sites to a left terminal group and a rightterminal group, respectively, in the formulas (1) to (4). Of thestructures shown below, (Y-2) or (Y-13) is more preferred in terms ofeasy synthesis.

In the formulas (1) to (4), each of Z¹, Z², Z³, and Z⁴ independentlyrepresents a monovalent organic group. The structure of the organicgroup is not particularly limited. Specific examples of the organicgroups include an alkyl group, a hydroxyl group, an alkoxy group, anaryloxy group, a heteroaryl oxy group, an alkyl thioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Ofthose, ones having the steric repulsion effect are preferred as theorganic groups represented by Z¹, Z², Z³, and Z⁴ from the viewpoint ofimproving the dispersibility. It is preferred that each of Z¹, Z², Z³,and Z⁴ independently represents an alkyl group with the number of carbonatoms from 5 to 24. Of those, it is particularly preferred that each ofZ¹, Z², Z³, and Z⁴ independently represents a branched alkyl group or acyclic alkyl group with the number of carbon atoms from 5 to 24.

In the formulas (1) to (4), each of n, m, D and q denotes an integer of1 to 500. In the formulas (1) and (2), each of j and k independentlydenotes an integer of 2 to 8. Each of j and k in the formulas (1) and(2) preferably denotes an integer of 4 to 6, most preferably 5, from theviewpoint of dispersion stability and development properties.

In the formula (3), R³ represents a branched or straight chain alkylenegroup, preferably an alkylene group having 1 to 10 carbon atoms, andmore preferably an alkylene group having 2 or 3 carbon atoms. In a casewhere p is 2 to 500, two or more R³ present may be the same or differentfrom each other.

In the formula (4), R⁴ represents a hydrogen atom or a monovalentorganic group. The monovalent organic group is not particularly limitedstructurally. Examples of R⁴ preferably include a hydrogen atom, analkyl group, an aryl group, and a heteroaryl group, and R⁴ is morepreferably a hydrogen atom or an alkyl group. In a case where R⁴ is analkyl group, a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, or a cyclic alkylgroup having 5 to 20 carbon atoms is preferred. A linear alkyl grouphaving 1 to 20 carbon atoms is more preferred. A linear alkyl grouphaving 1 to 6 carbon atoms is particularly preferred. In the formula(4), in a case where q is 2 to 500, X⁵ and R⁴, a plurality of eachpresent in a graft copolymer, may be the same or different from eachother.

In the polymer compound (B1), the structural units represented by theformulas (1) to (4) are preferably contained in a range of 10% to 90% interms of mass with respect to the total mass of the polymer compound(B1), more preferably in a range of 30% to 70%. In the case where thestructural units represented by the formulas (1) to (4) are containedwithin this range, the dispersibility of the titanium black particles ishigh and the development properties at the time of forming thelight-shielding layer 11 is excellent.

The polymer compound (B1) may have two or more types of structural unitswhich differ from each other in structure and each having a graftpolymer. In other words, the structural units represented by theformulas (1) to (4), which differ from each other in structure, may becontained in molecules of the polymer compound (B1). In the formulas (1)to (4), in a case where each of n, m, p, and q denotes an integergreater than or equal to 2, j and k may contain different structures inthe side chains of the formulas (1) and (2), respectively. In theformulas (3) and (4), a plurality of R³, R⁴, and R⁵, which are presentin the molecules, may be the same or different from each other.

As for the structural unit represented by the above-described formula(1), a structural unit represented by the following formula (1A) is morepreferred from the viewpoint of dispersion stability and developmentproperties. As for the structural unit represented by theabove-described formula (2), a structural unit represented by thefollowing formula (2A) is more preferred from the viewpoint ofdispersion stability and development properties.

In the formula (1A), X¹, Y², Z² and n are synonymous with X¹, Y², Z² andn in the above formula (1), and the preferred ranges are the same. Inthe formula (2A), X², Y², Z² and m are synonymous with X², Y², Z² and min the above formula (2), and the preferred ranges are the same.

As for the structural unit represented by the above formula (3), astructural unit represented by a formula (3A) or (3B) described below ismore preferred from the viewpoint of dispersion stability anddevelopment properties.

In the formula (3A) or (3B), X³, Y³, Z³ and p are synonymous with X³,Y³, Z³ and p in the formula (3), and the preferred ranges are the same.

It is more preferred that polymer compound (B1) has the structural unitrepresented by the above formula (1A) as the structural unit having agraft polymer.

In the polymer compound (B1), it is preferred that the structural unithaving a graft polymer is contained in a range of 10% to 90%, in termsof mass, with respect to the total mass of the polymer compound (B), andmore preferably 30% to 70%. In the case where the structural unit havinga graft chain is contained within this range, the dispersibility of thetitanium black particles is high and the development properties at thetime of forming the light-shielding layer 11 is excellent.

As described above, the polymer compound (B1) has a hydrophobicstructural unit which differs from the structural unit having a graftchain (that is, which does not correspond to the structural unit havinga graft chain). In the present invention, the hydrophobic structuralunit is a structural unit with no acid group (e.g. a carboxylic acidgroup, a sulfonic acid group, a phosphate group, a phenolic hydroxylgroup, or the like).

The hydrophobic structural unit is preferably a structural unit which isderived from (corresponds to) a compound (monomer) having the ClogPvalue of 1.2 or more, and more preferably a structural unit derived froma compound having the ClogP value of 1.2 to 8. Thereby, the effects ofthe present invention are expressed with more reliability.

A ClogP value is a value calculated by the program “CLOGP”, which isavailable from Daylight Chemical Information System, Inc. This programprovides values of “calculated logP” calculated using Hansch and Leo'sfragment approach (see documents below). The fragment approach is basedon the chemical structure of a compound, and divides the chemicalstructure into partial structures (fragments) and sums the logPcontribution allocated to each fragment. Thereby the logP value of thecompound is estimated. The details thereof are described in thefollowing documents. In the present invention, the ClogP valuescalculated by the program CLOGP v4.82 are used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G.Sammnens, J. B. Taylor andC. A. Ramsden, Eds., p. 295, Pergamon Press,1990 C. Hansch &A. J. Leo. Substituent Constants For CorrelationAnalysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo.Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

The term logP refers to the common logarithm of a partition coefficientP. The logP is a physical value representing how an organic compound isdistributed in an equilibrium of the two-phase system of oil (typically1-octanol) and water in a quantitative numeric value. The logP isexpressed in the following expression.log P=log(Coil/Cwater)

In the expression, Coil represents the molar concentration of thecompound in the oil phase, and Cwater represents the molar concentrationof the compound in the aqueous phase. Oil solubility increases as thevalue of logP crosses zero and increases in the positive direction andwater solubility increases as an absolute value increases in thenegative direction. The logP has a negative correlation with thewater-solubility of the organic compound and is widely used as aparameter for estimating the hydrophilic or hydrophobic properties of anorganic compound.

It is preferred that the polymer compound (B1) has at least one type ofstructural unit, being the hydrophobic structural unit, selected fromthe structural units derived from monomers represented by the followingformulas (i) to (iii).

In the above formulas (i) to (iii), each of R¹, R², and R³ independentlyrepresents a hydrogen atom, a halogen atom (e.g. fluorine, chlorine,bromine, or the like), or an alkyl group (e.g. a methyl group, an ethylgroup, a propyl group, or the like) having 1 to 6 carbon atoms.

Each of R¹, R², and R³ is more preferably a hydrogen atom or an alkylgroup having 1 to 3 carbon atoms, most preferably a hydrogen atom or amethyl group. It is particularly preferred that each of R² and R³ is ahydrogen atom. X represents an oxygen atom (—O—) or an imino group(—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. Examples of the divalentlinking groups include a divalent aliphatic group (e.g. an alkylenegroup, a substituted alkylene group, an alkenylene group, a substitutedalkenylene group, alkynylene group, or a substituted alkynylene group),a divalent aromatic group (e.g. an arylene group or a substitutedarylene group), a divalent heterocyclic group, and a combination of oneof the above and an oxygen atom (—O—), a sulfur atom (—S—), an iminogroup (—NH—), a substituted imino group (—NR³¹—, wherein R³¹ is analiphatic group, an aromatic group, or a heterocyclic group) or acarbonyl group (—CO—).

The divalent aliphatic group may have a cyclic structure or a branchedstructure. The number of carbon atoms in the aliphatic group ispreferably 1 to 20, more preferably 1 to 15, and still more preferably 1to 10. The aliphatic group may be a saturated aliphatic group or anunsaturated aliphatic group, but is preferably a saturated aliphaticgroup. Further, the aliphatic group may have a substituent. Examples ofthe substituents include a halogen atom, an aromatic group, and aheterocyclic group.

The number of carbon atoms in the divalent aromatic group is preferably6 to 20, more preferably 6 to 15, and most preferably 6 to 10. Thearomatic group may have a substituent. Examples of the substituentsinclude a halogen atom, an aliphatic group, an aromatic group, and aheterocyclic group.

The divalent heterocyclic group preferably has a 5- or 6-membered ringas the hetero ring. Another heterocyclic ring, an aliphatic ring, or anaromatic ring may be condensed with the heterocyclic ring. Theheterocyclic group may have a substituent. Examples of the substituentsinclude a halogen atom, a hydroxy group, an oxo group (═O), a thioxogroup (═S), an imino group (═NH), a substituted imino group (═N—R³²,wherein R³² represents an aliphatic group, an aromatic group, or aheterocyclic group), an aliphatic group, an aromatic group, and aheterocyclic group.

L is preferably a single bond or a divalent linking group containing analkylene group or an oxyalkylene structure. The oxyalkylene structure ismore preferably an oxyethylene structure or an oxypropylene structure.Furthermore, L may contain a polyoxyalkylene structure containing two ormore repeating oxyalkylene structures. The polyoxyalkylene structure ispreferably a polyoxyethylene structure or a polyoxypropylene structure.The polyoxyethylene structure is represented by —(OCH₂CH₂)n-, and n ispreferably an integer of 2 or more, and more preferably an integer of 2to 10.

Examples of Z include an aliphatic group (e.g. an alkyl group, asubstituted alkyl group, an unsaturated alkyl group, or a substitutedunsaturated alkyl group), an aromatic group (e.g. an arylene group or asubstituted arylene group), a heterocyclic group, and a combination ofone of the above and an oxygen atom (—O—), a sulfur atom (—S—), an iminogroup (—NH—), a substituted imino group (—NR³¹—, here R³¹ represents analiphatic group, an aromatic group, or a heterocyclic group), or acarbonyl group (—CO—), and the like.

The above-described aliphatic group may have a cyclic structure or abranched structure. The number of carbon atoms in the aliphatic group ispreferably 1 to 20, more preferably 1 to 15, still more preferably 1 to10. Furthermore a ring assembly hydrocarbon group or a crosslinkedcyclic hydrocarbon ring is included. Examples of the ring assemblyhydrocarbon groups include bicyclohexyl group, perhydronaphthalenylgroup, biphenyl group, and 4-cyclohexyl phenyl group. Examples of thecrosslinked cyclic hydrocarbon rings include bicyclic hydrocarbon ringssuch as pinane, bornane, norpinane, norbornane, bicyclooctane ring(bicyclo[2.2.2] octane ring, bicyclo[3.2. 1] octane ring, and the like),tricyclic hydrocarbon rings such as homobredane, adamantane,tricyclo[5.2.1.0^(2, 6)] decane, tricyclo[4.3.1.1^(2, 5)] undecane ring,and tetracyclic hydrocarbon rings such as tetracyclic[4.4.0.1^(2,5).1^(7,10)] dodecane, perhydro-1,4-methano-5, 8 methanonaphthalene ring and the like. In addition, the crosslinked cyclichydrocarbon rings include fused cyclic hydrocarbon rings which aremultiple fused rings of 5- to 8-membered cycloalkane rings such asperhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene,perhydroacenaphthene, perhydrofluorene, perhydroindene, andperhydrophenalene ring.

As for the aliphatic group, saturated aliphatic group is preferred tounsaturated aliphatic group. The aliphatic group may have a substituent.Examples of the substituents include a halogen atom, an aromatic group,and a heterocyclic group. However, the aliphatic group contains no acidgroup as a substituent.

The number of carbon atoms in the above-mentioned aromatic group ispreferably 6 to 20, more preferably 6 to 15, and most preferably 6 to10. The aromatic group may have a substituent. Examples of thesubstituents include a halogen atom, an aliphatic group, an aromaticgroup, and a heterocyclic group. However, the aromatic group has no acidgroup as a substituent.

The above-mentioned heterocyclic group preferably has a 5- or 6-memberedring as the heterocyclic ring. Another heterocyclic ring, aliphaticring, or aromatic ring may be condensed with the heterocyclic ring. Theheterocyclic group may have a substituent. Examples of the substituentsinclude a halogen atom, a hydroxy group, an oxo group (═O), a thioxogroup (═S), an imino group (═NH), a substituted imino group (═N—R³²,wherein R³² is an aliphatic group, an aromatic group, or a heterocyclicgroup), an aliphatic group, an aromatic group, and a heterocyclic group.However, the heterocyclic group has no acid group as a substituent.

In the formula (iii), each of R⁴, R⁵, and R⁶ independently represents ahydrogen atom, a halogen atom (e.g. fluorine, chlorine, or bromine), analkyl group with 1 to 6 carbon atoms (e.g. a methyl group, an ethylgroup, or a propyl group), Z, or -L-Z. Here, L and Z are synonymous withthose defined above. As for R⁴, R⁵, and R⁶, a hydrogen atom or an alkylgroup having 1 to 3 carbon atoms is preferred, and an a hydrogen atom ismore preferred.

In the present invention, as for a monomer represented by the generalformula (i), a compound in which each of R1, R2, and R3 is a hydrogenatom or a methyl group and L is an alkylene group or divalent linkinggroup containing oxyalkylene structure and X is an oxygen atom or animino group and Z is an aliphatic group, a heterocyclic group, or anaromatic group is preferred.

As for the monomer represented by the general formula (ii), a compoundin which R¹ is a hydrogen atom or a methyl group and L is an alkylenegroup and Z is an aliphatic group, a heterocyclic group, or an aromaticgroup and Y is a methine group is preferred. As for the monomerrepresented by the general formula (iii), a compound in which each ofR4, R5, and R6 is a hydrogen atom or a methyl group and Z is analiphatic group, a heterocyclic group, or an aromatic group ispreferred.

Examples of representative compounds represented by the formulas (i) to(iii) include radical polymerizable compounds selected from acrylic acidesters, methacrylic acid esters, and styrenes.

Specific examples of acrylic acid esters such as alkyl acrylate(preferably having 1 to 20 carbon atoms in the alkyl group) includebenzyl acrylate, 4-biphenyl acrylate, butyl acrylate, sec-butylacrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, octyl acrylate,dodecyl acrylate, 4-chlorophenyl acrylate, pentachlorophenyl acrylate,trifluoromethyl methyl acrylate, tridecane fluoro-hexyl ethyl acrylate4-cyano benzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate,2-ethoxyethyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, heptylacrylate, hexyl acrylate, isobornyl acrylate, isopropyl acrylate, methylacrylate, 3,5-dimethyl adamantyl acrylate, 2-naphthyl acrylate,neopentyl acrylate, fluorenyl acrylate, phenethyl acrylate, phenylacrylate, propyl acrylate, tolyl acrylate, amyl acrylate,tetrahydrofurfuryl acrylate, allyl acrylate, 2-allyloxyethyl acrylate,propargyl acrylate, adamantyl acrylate, and the like.

Examples of methacrylic acid esters such as alkyl methacrylate(preferably having 1 to 20 carbon atoms in the alkyl group) includebenzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate,sec-butyl methacrylate, t-butyl methacrylate, 4-t-butyl phenylmethacrylate, octyl methacrylate, dodecyl methacrylate, 4-chlorophenylmethacrylate, pentachlorophenyl methacrylate, trifluoromethyl methylmethacrylate, tridecane fluoro-hexyl ethyl methacrylate, 4-cyanophenylmethacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate,2-ethoxyethyl methacrylate, ethyl methacrylate, 2-ethylhexylmethacrylate, heptyl methacrylate, hexyl methacrylate, isobornylmethacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate,fluorenyl methacrylate, phenethyl methacrylate, phenyl methacrylate,propyl methacrylate, tolyl methacrylate, amyl methacrylate,tetrahydrofurfuryl methacrylate, allyl methacrylate, 2-allyloxyethylmethacrylate, propargyl methacrylate, adamantyl methacrylate, and thelike.

Examples of styrenes include styrenes, alkyl styrenes, alkoxy styrenes,halogenated styrenes, and the like. The examples of the alkyl styrenesinclude methyl styrene, dimethyl styrene, trimethyl styrene, ethylstyrene, diethyl styrene, isopropyl styrene, butyl styrene, hexylstyrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethylstyrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethylstyrene, and the like. Examples of the alkoxy styrenes include methoxystyrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, and the like.The examples of the halogenated styrenes include chlorostyrene,dichlorostyrene, trichlorostyrene, tetrachlorostyrene,pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene,fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene,4-fluoro-3-trifluoromethyl styrene, and the like.

Of these radical polymerizable compounds, preferably used aremethacrylic acid esters and styrenes. Particularly preferably used arebenzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate,pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyclohexylmethacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornylmethacrylate, isopropyl methacrylate, methyl methacrylate, 3, 5-dimethyladamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate,phenyl methacrylate, tetrahydrofurfuryl methacrylate, allylmethacrylate, styrene, methyl styrene, dimethyl styrene, trimethylstyrene, isopropyl styrene, butyl styrene, cyclohexyl styrene,chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene,acetoxymethyl styrene, methoxy styrene, 4-methoxy-3-methyl styrene,chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene,pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene,fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene,4-fluoro-3-trifluoromethyl styrene, 1-vinyl naphthalene, and 2-vinylnaphthalene.

Of the monomers corresponding to the hydrophobic structural unit, thecompounds containing heterocyclic group are as follows.

In the polymer compound (B1), it is preferred that the hydrophobicstructural unit is contained in a range of 10% to 90%, in terms of mass,with respect to the total mass of the polymer compound (B1), morepreferably in a range of 20% to 80%. In the case where the content iswithin the above-mentioned range, a sufficient pattern formation isachieved.

The polymer compound (B1) is capable of introducing a functional groupcapable of interacting with the titanium black. Here, it is preferredthat the polymer compound (B1) has a structural unit having a functionalgroup capable of interacting with the titanium black. Examples of thefunctional groups capable of interacting with the titanium blackparticles include an acid group, a basic group, a coordinating group,and a reactive functional group.

In a case where the polymer compound (B1) or the dispersant (B) has theacid group, the basic group, the coordinating group, or the reactivefunctional group, it is preferably in a form of a structural unit havingthe acid group, a structural unit having the basic group, a structuralunit having the coordinating group, or a structural unit having thereactivity, respectively. In particular, by further containing analkali-soluble group, such as a carboxylic acid group, as an acid group,the polymer compound (B1) is provided with developing properties forpattern formation through alkali development. In other words, byintroducing the alkali-soluble group to the polymer compound (B1), thepolymer compound (B1), being the dispersant indispensable for thedispersion of the titanium black particles, in the dispersioncomposition of the present invention has alkali-solubility. Thepolymerizable composition containing such dispersion composition isexcellent in light-shielding properties in the exposure step, andimproves alkali-developing properties of an unexposed portion.

By having a structural unit having an acid group, the polymer compound(B1) has an affinity for the solvent (C), so that the coating propertiesalso tend to improve. It is assumed that the acid group in thestructural unit having the acid group is likely to interact with thetitanium black, being the black colorant (A), so that the polymercompound (B1) disperses the titanium black stably. In addition, it isassumed that the viscosity of the polymer compound (B1) for dispersingthe titanium black is reduced by the above-described graft chain havingthe polyester structure, so that the polymer compound (B1) itself islikely to be dispersed stably.

The structural unit having the alkali-soluble group as the acid groupmay be the same as or different from the above-described structural unithaving the graft chain. However, the structural unit having thealkali-soluble group as the acid group differs from the above-describedhydrophobic structural unit (i.e. the structural unit having thealkali-soluble group as the acid group does not correspond to thehydrophobic structural unit described above).

Examples of the acid groups, being the functional groups capable ofinteracting with the titanium black, include a carboxylic acid group, asulfonic acid group, a phosphate group, and a phenolic hydroxyl group.Preferred is at least one of the carboxylic acid group, the sulfonicacid group, and the phosphate group. Particularly preferred is thecarboxylic acid group, which has excellent adsorption force to thetitanium black particles and high dispersion properties. In other words,it is preferred that the polymer compound (B1) further contains astructural unit having at least one of the carboxylic acid group, asulfonic acid group, and a phosphate group.

The polymer compound (B1) may have one or two or more types ofstructural units having an acid group. The polymer compound (B1) may ormay not contain a structural unit having an acid group. In the casewhere the polymer compound (B1) contains a structural unit having anacid group, a content of the structural unit having an acid group ispreferably 5% to 80%, in terms of mass, with respect to the total massof the polymer compound (B1), more preferably 10% to 60% from theviewpoint of inhibiting damage to image intensity caused by the alkalidevelopment described below.

Examples of the basic groups, being the functional groups capable ofinteracting with the titanium black, include a primary amino group, asecondary amino group, a tertiary amino group, a hetero ring containingN atom, and an amide group. Particularly preferred is the tertiary aminogroup, which has excellent adsorption force to the titanium black andhigh dispersibility thereof. The polymer compound (B1) can contain oneor more of such basic groups.

The polymer compound (B1) may or may not contain a structural unithaving a basic group. In the case where the polymer compound (B1)contains it, the content (in terms of mass) of the structural unithaving a basic group, with respect to the total mass of the polymercompound (B1) is preferably 0.01% to 50%, and more preferably 0.01% to30% from the viewpoint of reducing the development inhibition.

The examples of the coordinating groups, being the functional groupscapable of interacting with the titanium black, and the reactivefunctional groups include an acetylacetoxy group, a trialkoxysilylgroup, an isocyanate group, acid anhydride, and acid chloride.Particularly preferred is the acetylacetoxy group, which has excellentadsorption force to the titanium black and high dispersibility. Thepolymer compound (B1) may have one or more types of these groups.

The polymer compound (B1) may or may not contain a structural unithaving a coordinating group or a structural unit having a reactivefunctional group. In the case where the polymer compound (B1) containsit, the content of the structural unit, in terms of mass, with respectto the total mass of the polymer compound (B1) is preferably 10% to 80%,and more preferably 20% to 60% from the viewpoint of reducing thedevelopment inhibition.

In the case where the polymer compound (B1) has a functional group,other than the graft chain, capable of interacting with the titaniumblack, the polymer compound (B1) may have the above-described functionalgroup capable of interacting with the various types of titanium black.How those functional groups are introduced is not particularly limited.However, it is preferred that the polymer compound (B1) has at least onetype of structural unit selected from the structural units derived frommonomers represented by the following general formulas (iv) to (vi).

In the general formulas (iv) to (vi), each of R¹¹, R¹², and R¹³independently represents a hydrogen atom, a halogen atom (e.g. afluorine atom, a chlorine atom, a bromine atom, or the like), or analkyl group (e.g. a methyl group, an ethyl group, or a propyl group)having 1 to 6 carbon atoms.

In the general formulas (iv) to (vi), it is more preferred that each ofR¹¹, R¹², and R¹³ independently represents a hydrogen atom or an alkylgroup having 1 to 3 carbon atoms. The hydrogen atom or the a methylgroup are most preferred. In the formula (iv), it is particularlypreferred that each of R¹² and R¹³ independently represents a hydrogenatom.

In the general formula (iv), X₁ represents an oxygen atom (—O—) or iminogroup (—NH—), and is preferably an oxygen atom. In the general formula(v), Y represents a methine group or a nitrogen atom.

In the general formulas (iv) to (v), L₁ represents a single bond or adivalent linking group. Examples of the divalent linking groups includea divalent aliphatic group (e.g. an alkylene group, a substitutedalkylene group, an alkenylene group, a substituted alkenylene group, analkynylene group, and a substituted alkynylene group), a divalentaromatic group (e.g. an arylene group and a substituted arylene group),a divalent heterocyclic group, and a combination of one of the above andat least one of an oxygen atom (—O—), a sulfur atom (—S—), an iminogroup (—NH—), a substituted imino bond (—NR^(31,)—, wherein R³¹, is analiphatic group, an aromatic group, or a heterocyclic group), and acarbonyl bond (—CO—).

The above-described divalent aliphatic group may have a cyclic structureor a branched structure. The number of carbon atoms in the aliphaticgroup is preferably 1 to 20, more preferably 1 to 15, and still morepreferably 1 to 10. As for the aliphatic group, a saturated aliphaticgroup is preferred to an unsaturated aliphatic group. The aliphaticgroup may have a substituent. Examples of the substituents include ahalogen atom, a hydroxyl group, an aromatic group, and a heterocyclicgroup.

The number of carbon atoms in the above-described divalent aromaticgroup is preferably 6 to 20, more preferably 6 to 15, and mostpreferably 6 to 10. The aromatic group may have a substituent. Examplesof the substituents include a halogen atom, a hydroxyl group, analiphatic group, an aromatic group, and a heterocyclic group.

The above-described divalent heterocyclic group preferably has a 5- or6-membered ring as the heterocyclic ring. One or more of anotherheterocyclic ring, aliphatic ring, or aromatic ring may be condensedwith the heterocyclic ring. The heterocyclic group may have asubstituent. Examples of the substituents include a halogen atom, ahydroxy group, an oxo group (═O), a thioxo group (═S), an imino group(═NH), a substituted imino group (═N—R³², wherein R³² represents analiphatic group, an aromatic group, or a heterocyclic group), aliphaticgroup, an aromatic group, and a heterocyclic group.

It is preferred that L₁ is a single bond or a divalent linking groupcontaining an alkylene group or an oxyalkylene structure. It is morepreferred that the oxyalkylene structure is an oxyethylene structure oran oxypropylene structure.

Furthermore, L may contain a polyoxyalkylene structure containing two ormore repeating oxyalkylene structures. As for the polyoxyalkylenestructure, a polyoxyethylene structure or a polyoxypropylene structureis preferred. The polyoxyethylene structure is represented by—(OCH₂CH₂)n- where n is preferably an integer of 2 or more, and morepreferably an integer of 2 to 10.

In the general formulas (iv) to (vi), Z₁ represents a functional group,other than the graft site, capable of interacting with the titaniumblack particles, and is preferably a carboxylic acid group or a tertiaryamino group, and more preferably a carboxylic acid group.

In the general formula (vi), each of R¹⁴, R¹⁵, and R¹⁶ independentlyrepresents a hydrogen atom, a halogen atom (e.g. fluorine, chlorine,bromine, or the like), an alkyl group having 1 to 6 carbon atoms (e.g. amethyl group, an ethyl group, a propyl group, or the like), —Z₁, or-L₁-Z₁. Here, L₁ and Z₁ are synonymous with L₁ and Z₁ described above,respectively, and the preferred examples are also the same. It ispreferred that each of R¹⁴, R¹⁵, and R¹⁶ independently represents ahydrogen atom or an alkyl group having 1 to 3 carbon atoms, and morepreferably a hydrogen atom.

In the present invention, as for the monomer represented by the generalformula (iv), preferred is a compound in which each of R¹¹, R¹², and R¹³independently represents a hydrogen atom or a methyl group, and L₁ is adivalent linking group containing an alkylene group or an oxyalkylenestructure, and X is an oxygen atom or an imino group, and Z is acarboxylic acid group.

As for a monomer represented by the general formula (v), preferred is acompound in which R¹¹ represents a hydrogen atom or a methyl group, andL₁ represents an alkylene group, and Z₁ represents a carboxylic acidgroup, and Y represents a methine group.

As for a monomer represented by the general formula (vi), preferred is acompound in which each of R¹⁴, R¹⁵, and R¹⁶ independently represents ahydrogen atom or a methyl group, and L is a single bond or an alkylenegroup, and Z is a carboxylic acid group.

The following shows typical examples of the monomers (compounds)represented by the general formulas (iv) to (vi). Examples of themonomers include methacrylic acid, crotonic acid, isocrotonic acid, areaction product of a compound (e.g. 2-hydroxyethyl methacrylate) havingaddition-polymerizable double bond and a hydroxyl group in molecules andsuccinic anhydride, a reaction product of a compound havingaddition-polymerizable double bond and a hydroxyl group in molecules andphthalic anhydride, a reaction product of a compound having anaddition-polymerizable double bond and a hydroxyl group in molecules andtetrahydroxy phthalic anhydride, a reaction product of a compound havingan addition-polymerizable double bond and a hydroxyl group in moleculesand trimellitic anhydride, a reaction product of a compound having anaddition-polymerizable double bond and a hydroxyl group in molecules andpyromellitic anhydride, acrylic acid, acrylic acid dimers, oligomers ofacrylic acid, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoicacid, vinyl phenol, 4-hydroxyphenyl methacrylamide, and the like.

From the viewpoint of interacting with the titanium black, thedispersion stability, and the permeability of a developer, the contentof the functional group capable of interacting with the titanium blackis preferably 0.05 mass % to 90 mass %, more preferably 1.0 mass % to 80mass %, and still more preferably 10 mass % to 70 mass % with respect tothe total mass of the polymer compound (B).

For the purpose of improving various properties such as image intensity,the polymer compound (B1) may further contain other structural units(e.g. a structural unit having a functional group with an affinity for adispersion medium used for a dispersion) having various functions whichdiffer from the structural unit having a graft chain, the hydrophobicstructural unit, and the structural unit having a functional groupcapable of interacting with the titanium black particles as long as itdoes not impair the effects of the present invention.

Examples of other structural units include a structural unit derivedfrom a radical polymerizable compound selected from acrylonitriles,methacrylonitriles, and the like.

The polymer compound (B1) may use one or two or more types of otherstructural units. The content thereof in terms of mass, with respect tothe total mass of the polymer compound (B1), is preferably 0% to 80%,and particularly preferably 10% to 60%. In the case where the content iswithin the above-described range, the sufficient pattern formationproperties are maintained.

The acid value of the polymer compound (B1) is preferably in the rangeof 0 mgKOH/g to 160 mgKOH/g, more preferably in the range of 10 mgKOH/gto 140 mgKOH/g, and still more preferably 20 mgKOH/g to 120 mg KOH/g.

In a case where the acid value of the polymer compound (B1) is less thanor equal to 160 mg KOH/g, peeling of the pattern during the developmentin forming the light-shielding layer 11 is more effectively inhibited,which will be described below. In a case where the acid value of thepolymer compound (B1) is 10 mgKOH/g or more, the alkali developmentproperty, which will be described below, is improved. In a case wherethe acid value of the polymer compound (B1) is 20 mgKOH/g or more,precipitation of the dispersoid such as the titanium black or thedispersoid containing the titanium black and the Si particles is furtherinhibited, the number of coarse particles is further reduced, and thetemporal stability of the dispersion composition and the polymerizationcomposition is further improved.

In the present invention, the acid value of the polymer compound (B1) iscalculated from the average content of the acid groups in the polymercompound (B1), for example. A resin having a desired acid value isobtained by changing the content of a structural unit containing an acidgroup, which is a constituent of the polymer compound (B1).

In the case of forming the light-shielding layer 11, the weight averagemolecular weight of the polymer compound (B1) in terms of polystyrenemeasured by GPC method in the present invention is preferably 4,000 to300,000, and more preferably 5,000 to 200,000, and still more preferably6,000 to 100,000, and particularly preferably 10,000 to 50,000, from theviewpoint of inhibiting peeling of the pattern during development andthe development properties.

The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation) andis based on a method using TSKgel SuperHZM-H, TSKgel SuperHZ4000, orTSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID×15 cm)as a column and THF (tetrahydrofuran) as an eluent.

The polymer compound (B1) is synthesized based on a known method.Examples of solvents used for synthesizing the polymer compound (B)include ethylene dichloride, cyclohexanone, methyl ethyl ketone,acetone, methanol, ethanol, propanol, butanol, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethylacetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide,toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like.These solvents may be used singly or in combination of two or more.

Specific examples of the polymer compounds (B1) include “Disperbyk-161,162, 163, 164, 165, 166, and 170 (trade name, polymeric copolymer)manufactured by BYK Co., “EFKA 4047, 4050, 4010, 4165 (trade name,polyurethane-based), EFKA 4330, 4340 (trade name, block copolymer)manufactured by EFKA, and the like. These polymer compounds (B) may beused singly or in combination of two or more.

The specific examples of the polymer compounds (B1) are described in thefollowing, but are not limited thereto. Note that, in the followingcompounds illustrated as examples, a numerical value written next toeach structural unit (a number written next to a repeating unit in amain chain) indicates the content of the structural unit (mass %:although written as “wt %” in the following). A numerical value writtennext to a repeating unit in a side chain indicates the number ofrepetition of the repeating unit.

The content of the polymer compound (B1) in the dispersion compositionwith respect to the total solid content (mass) of the dispersioncomposition is preferably 1 mass % to 90 mass %, and more preferably 3mass % to 70 mass %. The content of the polymer compound (B1) in thepolymerizable composition with respect to the total solid content (mass)of the polymerizable composition is preferably 0.1 mass % to 50 mass %,more preferably 0.5% to 30 wt %.

<(B2) Resin Different from Polymer Compound (B1)>

The dispersion composition and the polymerizable composition may containa polymer compound (B2) which differs from the polymer compound (B1) (inother words, which does not correspond to the polymer compound (B1)).The preferred range of the weight average molecular weight of thepolymer compound (B2) is similar to that of the polymer compound (B1)described above.

Specific examples of the polymer compounds (B2) include “Disperbyk-101(trade name, polyamidoamine phosphate), 107 (trade name, carboxylic acidester), 110 (trade name, copolymer containing acid group), 130 (tradename, polyamide), 180 (trade name, polymeric copolymer), BYK-P104, P105(trade name, high molecular weight unsaturated polycarboxylic acid)”manufactured by BYK, “EFKA4400, 4402 (trade name, modifiedpolyacrylate), 5010 (polyester amide), 5765 (trade name, high molecularweight polycarboxylate), 6220 (trade name, fatty acid polyester), 6745(trade name, phthalocyanine derivative), 6750 (trade name, azo pigmentderivative)” manufactured by EFKA Co., “AJISPER PB821, PB822”manufactured by Ajinomoto Fine-Techno Co., Ltd., “FLOWLEN TG-710(urethane oligomer), POLYFLOW No. 50E, No. 300 (trade name, acryliccopolymer)” manufactured by Kyoeisha Chemical Co., Ltd., “DisparlonKS-860, 873SN, 874, #2150 (trade name, aliphatic polycarboxylic acid),#7004 (polyether ester), DA-703-50, DA-705, DA-725” manufactured byKusumoto Kasei Co., Ltd., “DEMOL RN, N (trade name, naphthalenesulfonicacid formaldehyde polycondensate), DEMOL MS, C, SN-B (trade name,aromatic sulfonic acid formaldehyde polycondensate), HOMOGENOL L-18(trade name, polymeric polycarboxylic acids), EMULGEN 920, 930, 935, 985(trade name, polyoxyethylene nonyl phenyl ether), ACETAMIN 86(stearylamine acetate)” manufactured by Kao Corporation, Ltd.,“SOLSPERSE 5000 (phthalocyanine derivative), 22000 (trade name, azopigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (tradename, polymers having functional units at the terminal ends), 24000,28000, 32000, 38500 (graft polymers)” manufactured by The LubrizolCorporation, “Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX(trade name, polyoxyethylene monostearate)” manufactured by NikkoChemicals, and the like and also include an amphoteric dispersant suchas Hinoakuto T-8000E manufactured by Kawaken Fine Chemical Co., Ltd.

The dispersion composition may or may not contain the polymer compound(B2). In the case where the dispersion composition contains the polymercompound (B2), the content of the polymer compound (B2) with respect tothe total solid mass content of the dispersion composition is preferably0.5 mass % to mass %, and more preferably 1 mass % to 20 mass %. Thepolymerizable composition of the present invention may or may notcontain the polymer compound (B2). In the case where the polymerizablecomposition contains the polymer compound (B2), the content of thepolymer compound (B2) with respect to the total mass content of thepolymerizable composition is preferably 0.1 mass % to 50 mass %, andmore preferably 0.5 mass % to 30 mass %.

<(C) Solvent>

The dispersion composition and the polymerizable composition of thepresent invention contains a solvent (C). It is preferred that thesolvent (C) is an organic solvent.

Examples of organic solvents include acetone, methyl ethyl ketone,cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran,toluene, ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol dimethyl ether, propylene glycol monomethylether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone,diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyleneglycol ethyl ether acetate, ethylene glycol mono-isopropyl ether,ethylene glycol monobutyl ether acetate, 3-methoxy propanol,methoxymethoxy ethanol, diethylene glycol monomethyl ether, diethyleneglycol monoethyl ether, diethylene glycol dimethyl ether, diethyleneglycol diethyl ether, propylene glycol monomethyl ether acetate,propylene glycol monoethyl ether acetate, 3-methoxy propyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate,butyl acetate, methyl lactate, and ethyl lactate, but are not limitedthereto.

The solvents may be used singly or in combination of two or more. In acase where two or more solvents are used in combination, particularlypreferred is a combination of two or more selected from theabove-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethylether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone,cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propyleneglycol methyl ether, and propylene glycol methyl ether acetate.

The amount of the solvent (C) contained in the dispersion compositionrelative to the total amount of the dispersion composition is preferably10 mass % to 80 mass %, more preferably 20 mass % to 70 mass %, andstill more preferably 30 mass % to 65 mass %. The amount of the solvent(C) contained in the polymerizable composition relative to the totalamount of the polymerizable composition is preferably 10 mass % to 90mass %, more preferably 20 mass % to 80 mass %, still more preferably 25mass % to 75 mass %.

<(D) Polymerizable Compound>

As described above, the polymerizable composition contains (D) apolymerizable compound. It is preferred that the polymerizable (D) hasat least one addition-polymerizable ethylenically unsaturated group andthe boiling point of 100° C. or more at normal atmospheric pressure.

Examples of compounds having at least one addition-polymerizableethylenically unsaturated group and the boiling point of 100° C. or moreat the normal atmospheric pressure include monofunctional acrylates ormethacrylates such as polyethylene glycol mono (meth) acrylate,polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth)acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri(meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritoltri (meth) acrylate, pentaerythritol tetra (meth) acrylate,dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate,trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl)isocyanurate, and (meth) acrylates of a compound obtained by addingethylene oxide or propylene oxide to polyfunctional alcohol such asglycerin or trimethylol ethane, poly (meth) acrylates of pentaerythritolor dipentaerythritol, urethane acrylates described in Japanese PatentApplication Publication No. 48-41708, Japanese Patent ApplicationPublication No. 50-6034, Japanese Patent Application Publication No.51-37193, polyester acrylates described in Japanese Patent ApplicationPublication No. 48-64183, Japanese Patent Application Publication No.49-43191, and Japanese Patent Unexamined Application Publication No.52-30490, polyfunctional acrylates such as epoxy acrylate, which is areaction product of epoxy resin and (meth) acrylic acid, andmethacrylates. In addition, photocurable monomers and oligomersdescribed on pages 300 to 308 in Journal of the Adhesion Society ofJapan, Vol. 20, No. 7 may also be used.

Furthermore, a compound, which is obtained by (meth)acrylation afteraddition of ethylene oxide or propylene oxide to the above-mentionedpolyfunctional alcohol, expressed by general formulas (1) and (2)described together with the specific examples in Japanese PatentLaid-Open Publication No. 10-62986 may be used.

Of those, preferred are dipentaerythritol penta (meth) acrylate,dipentaerythritolhexa (meth) acrylate, and structures in which theacryloyl groups thereof are linked to dipentaerythritol via an ethyleneglycol residue or a propylene glycol residue. Oligomer types thereof mayalso be used.

Also preferred are urethane acrylates described in Japanese PatentExamined Application Publication No. 48-41708, Japanese PatentUnexamined Application Publication No. 51-37193, Japanese PatentExamined Application Publication Nos. 2-32293 and 2-16765, and urethanecompounds having an ethylene oxide-based skeleton described in JapanesePatent Examined Application Publication Nos. 58-49860, 56-17654,62-39417, and 62-39418. A photopolymerizable composition excellent inphotosensitive speed is obtained by using an addition polymerizablecompound having an amino structure or a sulfide structure in a moleculeas described in Japanese Patent Unexamined Application Publication Nos.63-277653, 63-260909, and 1-105238. Examples of commercially availableproducts include urethane oligomer UAS-10, UAB-140 (trade names,manufactured by Nippon Paper Chemicals Ltd.), UA-7200 manufactured byShin-Nakamura Chemical Industry Co., Ltd., DPHA-40H (trade name,manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-3061,AH-600, T-600, AI-600 (trade names, manufactured by Kyoeisha ChemicalCo., Ltd.), and the like.

Also preferred are ethylenically unsaturated compounds having an acidgroup. Examples of commercially available products include TO-756(carboxyl group-containing trifunctional acrylate) and TO-1382 (carboxylgroup-containing pentafunctionalacrylate) manufactured by TOAGOSEI Co.,Ltd., and the like. As for the polymerizable compound used for thepresent invention, tetra or higher functional acrylate compounds arepreferred.

The polymerizable compound (D) may be used singly or in combination oftwo or more. In the case where a combination of two or morepolymerizable compounds is used, the combination is determined asappropriate in accordance with the physical properties or the likerequired for the polymerizable compound. Examples of the preferredcombinations of the polymerizable compounds may be a combination of twoor more types of polymerizable compounds selected from theabove-mentioned polyfunctional acrylate compounds, e.g. a combination ofdipentaerythritolhexaacrylate and pentaerythritol triacrylate.

The content of the polymerizable compound (D) in the polymerizablecomposition of the present invention with respect to the total solidcontent of the polymerizable composition is preferably 3 mass % to 55mass %, and more preferably 10 mass % to 50 mass %.

<(E) Polymerization Initiator>

The polymerizable composition contains (E) polymerization initiator(preferably a photoinitiator) as described above. The polymerizationinitiator (E) is a compound which is decomposed by light or heat andinitiates and promotes the polymerization of the above-mentionedpolymerizable compound (D). It is preferred that the polymerizationinitiator (E) absorbs light in the wavelength range of 300 to 500 nm.

Specific examples of the polymerization initiators (E) include organichalogenated compounds, oxydiazole compounds, carbonyl compounds, ketalcompounds, benzoin compounds, organic peroxide compounds, azo compounds,coumarin compounds, azide compounds, metallocene compounds, organicborate compounds, disulfonic acid compounds, oxime compounds (inparticular oxime ester compounds), onium salt compounds, and acylphosphine (oxide) compounds. More specific examples include apolymerization initiator described in paragraphs [0081] to [0100] and[0101] to [0139] of Japanese Patent Unexamined Application PublicationNo. 2006-78749. Of the above polymerization initiators, the oximecompounds (in particular the oxime ester compounds) are more preferredfrom the viewpoint of improving the shape of the pattern obtained. Asfor the oxime compounds, IRGACURE OXE01 and OXE02 manufactured by CibaSpecialty Chemicals Inc. are preferred. OXE01 and OXE02 provide the sameeffects.

The content of the polymerization initiator (E) in the polymerizablecomposition is preferably 0.1 mass % to 30 mass %, and more preferably 1mass % to 25 mass %, and still more preferably 2 mass % to 20 mass %with respect to the total solid content of the polymerizablecomposition.

[(F) Other Additives]

In addition to the dispersion composition of the present invention, thepolymerizable compound (D), and the polymerization initiator (E),various additives may be added to the polymerizable compositiondepending on the purpose.

(F-1) Binder Polymer

The polymerizable composition may further contain a binder polymer (F-1)as necessary for the purpose of improving coating properties and thelike. It is preferred to use a linear organic polymer as the binderpolymer (F-1). Any known “linear organic polymer” may be usedarbitrarily. Preferably, a linear organic polymer which is soluble orswellable in water or weakly alkaline water is chosen so as to allowwater development or weakly alkaline water development. The linearorganic polymer is used not only as a film-forming agent, but selectedand used in accordance with a developer (developing agent) composed ofwater, weak alkaline water, or an organic solvent.

For example, the use of a water-soluble organic polymer allows waterdevelopment. Examples of such linear organic polymers include radicalpolymers having a carboxylic acid group in a side chain described in,for example, Japanese Patent Unexamined Application Publication No.59-44615, Japanese Patent Examined Application Publication No. 54-34327,Japanese Patent Examined Application Publication No. 58-12577, JapanesePatent Examined Application Publication No. 54-25957, Japanese PatentUnexamined Application Publication No. 54-92723, Japanese PatentUnexamined Application Publication No. 59-53836, and Japanese PatentUnexamined Application Publication No. 59-71048, i.e. a resin havingcarboxyl group-containing monomers alone or copolymerized, a resinobtained by hydrolysis, half-esterification, or half-amidation of anacid anhydride unit having acid anhydride-containing monomers alone orcopolymerized, and epoxy acrylate obtained by modifying epoxy resin withunsaturated monocarboxylic acid and acid anhydride, and the like.Examples of the carboxyl group-containing monomers include acrylic acid,methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaricacid, 4-carboxyl styrene, and the like. Examples of the acidanhydride-containing monomers include maleic anhydride acid, and thelike. Also, acidic cellulose derivatives having a carboxylic acid groupin a side chain. In addition to those described above, a compoundobtained by adding cyclic acid anhydride to a polymer having a hydroxylgroup is useful.

Urethane binder polymers containing an acid group described in JapanesePatent Unexamined Application Publication Nos. 7-12004, 7-120041,7-120042, 8-12424, 63-287944, 63-287947, 1-271741, 10-116232, and thelike are advantageous in terms of suitability for low exposure becausethey are excellent in strength.

Also preferred are acetal-modified polyvinyl alcohol binder polymershaving an acid group described in European Patent No. 993966, EuropeanPatent No. 1204000, Japanese Patent Application No. 2001-318463, and thelike, due to an excellent balance between the film strength anddevelopability. In addition to those described above, polyvinylpyrrolidone, polyethylene oxide, and the like are useful as thewater-soluble linear organic polymers. Also, alcohol-soluble nylon,polyether of 2, 2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, andthe like are useful in order to increase the strength of the cured film.

In particular, of those described above, [benzyl (meth) acrylate/(meth)acrylic acid/other addition polymerizable vinyl monomer as necessary]copolymers and [allyl (meth) acrylate/(meth) acrylic acid/other additionpolymerizable vinyl monomer as necessary] copolymers are preferred dueto the excellent balance among the film strength, the sensitivity, andthe developability.

The weight average molecular weight of the binder polymer (F-1) used inthe polymerizable composition is preferably 1,000 to 300,000, morepreferably 1,500 to 250,000, still more preferably from 2,000 to200,000, and particularly preferably 2,500 to 100,000 from the viewpointof inhibiting peeling of the pattern and from the viewpoint ofdevelopability. The number average molecular weight of the binderpolymer (F-1) is preferably 1,000 or more, and more preferably in therange of 1500 to 250,000. The polydispersity (weight average molecularweight/number average molecular weight) of the binder polymer (F-1) ispreferably 1 or more, and more preferably in the range of 1.1 to 10.Here, the weight average molecular weight of the binder polymer (F-1) ismeasured by GPC, for example.

The binder polymer (F-1) described above may be any one of a randompolymer, a block polymer, a graft polymer, and the like.

The binder polymer (F-1) used in the present invention is synthesized byconventional and known methods. Examples of solvents used at the time ofthe synthesis include tetrahydrofuran, ethylene dichloride,cyclohexanone, and the like. These solvents are used singly or incombination of two or more. Examples of radical polymerizationinitiators used at the time of synthesizing the binder polymer (F-1)include known compounds such as azo initiators and peroxide initiators.

In the present invention, an alkali-soluble resin having a double bondin a side chain is used as the binder polymer (F-1). Thereby, both thecure extent (curability) of the exposed portion and the alkalidevelopability of the unexposed portion are particularly improved. Thealkali-soluble resin having a double bond in a side chain has an acidgroup for making the resin alkali-soluble and at least one unsaturateddouble bond in its structure, thereby improving various types ofperformance such as removability of a non-image portion. The resinhaving such structure is described in detail in Japanese PatentUnexamined Application Publication No. 2003-262958 and the resindescribed therein may be used as the binder polymer of the presentinvention.

Cardo resin may be used as the binder polymer (F-1). The cardo resinwhich is selected from a group consisting of epoxy resin, polyesterresin, polycarbonate resin, acrylic resin, polyether resin, polyamideresin, polyurea resin, and polyimide resin, and has a fluorene skeletonis preferred. Here, the cardo resin refers to the resin which has cardostructure (skeleton structure in which two annular structures arecombined with the quaternary carbon atom which constitutes the annularstructure) in a molecule. More specifically, the compound described inparagraphs [0046] to [0057] of Japanese Patent Unexamined ApplicationPublication No. 2011-170334 may be used.

The content of the binder polymer in the polymerizable composition withrespect to the total solid content of the composition is preferably 0.1mass % to 25 mass %, and from the viewpoint of inhibiting peeling of thelight-shielding layer 11 and reducing the development residues, morepreferably 0.3 mass % to 20 mass % and still more preferably 1.0 to 15mass %.

(F-2) Colorant

In order to express desired light-shielding properties, thepolymerizable composition may contain a colorant (F-2) such as a knownorganic pigment or dye other than inorganic pigment in combination withanother colorant.

Examples of organic pigments used as the colorants (F-2), which can beused in combination with another colorant, includes the pigmentdescribed in paragraphs [0030] to [0044] described in Japanese PatentUnexamined Application Publication No. 2008-224982, C. I. Pigment Green58 and C. I. Pigment Blue 79 with a Cl substituent substituted with OH.Of those described above, the pigments preferably used are listed asfollows; however, the colorants (F-2) applicable to the presentinvention are not limited thereto.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154,167, 180, 185,

C. I. Pigment Orange 36, 38, 62, 64,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255,

C. I. Pigment Violet 19, 23, 29, 32,

C. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66,

C. I. Pigment Green 7, 36, 37, 58,

C. I. Pigment Black 1

Examples of dyes used as the colorants (F-2) are not particularlylimited and known dyes may be selected and used as necessary, forexample, pigments described in Japanese Patent Unexamined ApplicationNos. 64-90403, 64-91102, H1-94301, and H6-11614, Japanese Patent No.2592207, U.S. Pat. Nos. 4,808,501, 5,667,920, and 5,059,500, JapanesePatent Unexamined Application Publication Nos. H5-333207, H6-35183,H6-51115, H6-194828, H8-211599, H4-249549, H10-123316, H11-302283,H7-286107, 2001-4823, H8-15522, H8-29771, H8-146215, H11-343437,H8-62416, 2002-14220, 2002-14221, 2002-14222, 2002-14223, H8-302224,H8-73758, H8-179120, H8-151531, and the like.

Examples of the chemical structures of the dyes include pyrazole azotype, aniline azo type, triphenylmethane type, anthraquinone type,anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azotype, pyridone azo type, cyanine type, phenothiazine type,pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type,benzopyran type, indigo type, pyrromethene type and the like.

As for the colorant (F-2) in the polymerizable composition, preferred isat least one type of organic pigment selected from the group consistingof an orange pigment, a red pigment, and a violet pigment from theviewpoint of compatibility between the curability and thelight-shielding properties in the case where the colorant (F-2) iscombined with the titanium black, which is essentially contained in thecomposition. The most preferred combination is a combination with a redpigment.

As for the orange pigment, the red pigment, and the violet pigment, forexample, various types of pigments which belong to the “C. I. PigmentOrange”, the “C. I. Pigment Red”, and the “C. I. Pigment Violet”described above may be selected depending on the requiredlight-shielding properties. In terms of improving the light-shieldingproperties, the C. I. Pigment Violet 29, the C. I. Pigment Orange 36,38, 62, 64, the C. I. Pigment Red 177, 254, 255, and the like arepreferred.

(F-3) Sensitizer

The polymerizable composition may contain an (F-3) sensitizer for thepurpose of improving radical generation efficiency of the polymerizationinitiator (E) and increasing the wavelength of a photosensitivewavelength. It is preferred that the sensitizer (F-3) sensitizes thepolymerization initiator (E) with an electron transfer mechanism or anenergy transfer mechanism. Preferred examples of the sensitizers (F-3)include a compound described in paragraphs [0085] to [0098] described inJapanese Patent Unexamined Application Publication No. 2008-214395.

The content of the sensitizer (F-3) with respect to the total solidcontent of the polymerizable composition is preferably in a range of 0.1mass % to 30 mass %, more preferably in a range of 1 to 20 mass %, andstill more preferably in a range of 2 to 15 mass % from the viewpoint ofsensitivity and storage stability.

(F-4) Polymerization inhibitor

It is preferred to add a small amount of a polymerization inhibitor(F-4) to the polymerizable composition of the present invention, duringthe manufacture or the storage of the polymerizable composition, for thepurpose of inhibiting unnecessary thermal polymerization of thepolymerizable compound. A known thermal polymerization inhibitor may beused as the polymerization inhibitor (F-4) and specific examples thereofinclude hydroquinone, p-methoxy phenol, di-t-butyl-p-cresol, pyrogallol,t-butyl catechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol),2,2′-methylenebis (4-methyl-6-t-butylphenol),N-nitrosophenylhydroxyamine cerous salt and the like. The content of thethermal polymerization inhibitor (F-4) with respect to the total solidcontent of the polymerizable composition is preferably approximately0.01 mass % to approximately 5 mass %.

As necessary, in order to prevent polymerization inhibition by oxygen,higher fatty acid derivative such as behenic acid or behenic acid amide,or the like may be added so as to unevenly distribute the higher fattyacid derivative or the like on the surface of the coating film in courseof drying after the coating. The amount of the higher fatty acidderivative to be added is preferably approximately 0.5 mass % toapproximately 10 mass % with respect to the total solid content.

(F-5) Adhesion Promoter

An adhesion promoter (F-5) may be added to the polymerizable compositionfor the purpose of improving the adhesion with a hard surface of asupport or the like. Examples of the adhesion promoters (F-5) include asilane coupling agent, a titanium coupling agent, and the like.

As for the silane coupling agent, preferred areγ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyl trimethoxy silane,γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, andγ-methacryloxypropyl trimethoxysilane.

The content of the adhesion promoter (F-5) is preferably 0.5 mass % to30 mass % and more preferably 0.7 mass % to 20 mass % with respect tothe total solid content of the polymerizable composition.

Note that in the case where the filter body 6, on which thelight-shielding layer 11 is formed by applying the polymerizablecomposition, is made from glass, it is preferred to add the adhesionpromoter (F-5) from the viewpoint of improving the sensitivity.

(F-6) Surfactant

Various types of surfactants may be added to the polymerizablecomposition from the viewpoint of improving coating properties. Varioustypes of surfactants such as fluorine-based surfactants, nonionic-basedsurfactants, cationic-based surfactants, anionic-based surfactants, andsilicone-based surfactants may be used as the surfactants.

In particular, liquid properties (particularly, fluidity) of thepolymerizable composition prepared as a coating liquid are improved bycontaining the fluorine-based surfactant. Thereby uniformity of thecoating thickness and liquid-saving properties are further improved. Inother words, in a case where a film is formed from a coating liquidwhich contains a polymerizable composition containing a fluorine-basedsurfactant, the interfacial tension between the coating liquid and theapplication surface is lowered, so that wettability to the applicationsurface is improved and thereby coating properties of the applicationsurface is improved. Therefore, it is effective in forming a film havinguniform thickness with small unevenness even in a case where a thin filmwith the thickness in the order of several μm is made with a smallliquid amount.

The content of fluorine in the fluorine-based surfactant is preferably 3mass % to 40 mass %, more preferably 5 mass % to 30 mass o, particularlypreferably 7 mass % to 25 mass %. The fluorine surfactant with thefluorine content within the above range is effective in terms ofuniformity in thickness of the coating film, liquid-saving properties,and has excellent solubility in the polymerizable composition.

Examples of the fluorine-based surfactants include Megafac F171, theF172, the F173, the F176, the F177, the F141, the F142, the F143, theF144, the R30, the F437, the F475, the F479, same F482, the F554, theF780, the F781 (manufactured by DIC Ltd.), Fluorad FC430, the FC431, theFC171 (manufactured by Sumitomo Co., Ltd.), SURFLON S-382, the SC-101,same SC-103, the SC-104, the SC-105, the SC1068, the SC-381, the SC-383,the 5393, the KH-40 (manufactured by Asahi Glass Co., Ltd.), and thelike.

Specific examples of the nonionic-based surfactants include glycerol,trimethylol propane, trimethylol ethane and their ethoxylates andpropoxylates (for example, glycerol propoxylate, glycerol ethoxylate,and the like), polyoxyethylene lauryl ether, polyoxyethylene stearylether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether,polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate,polyethylene glycol distearate, sorbitan fatty acid ester (BASF Corp.,Pluronic L10, L31, L61, L62, 10R5, 17R2, 25 R2, tetronic 304, 701, 704,901, 904, 150R1, SOLSPERSE 20000 (manufactured by Nippon LubrizolCorporation, Ltd.), and the like.

Specific examples of the cationic-based surfactants includephthalocyanine derivatives (trade name: EFKA-745, manufactured byMorishita Sangyo, Ltd.), organosiloxane polymers KP341 (Shin-EtsuChemical Co., Ltd.), (meth) acrylic acid based (co) polymer POLYFLOW No.75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd.), W001 (manufactured byYusho Co., Ltd.), and the like.

Specific examples of the anionic-based surfactants include W004, W005,and W017 (manufactured by Yusho Co., Ltd.), and the like.

Examples of the silicone-based surfactants include “Toray SiliconeDC3PA”, “Toray silicone SH7PA”, “Toray silicone DC11PA”, “Toray siliconeSH21PA”, “Toray silicone SH28PA”, “Toray silicone SH29PA”, “Toraysilicone SH30PA”, and “Toray Silicone SH8400” manufactured by DowCorning Toray, Ltd., “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, and“TSF-4452” manufactured by Momentive Performance Materials Inc.,“KP341”, “KF6001”, and “KF6002” manufactured by Shin-Etsu Silicone Co.,Ltd., “BYK307”, “BYK323”, and “BYK330” manufactured by BYK Co., and thelike.

The surfactants may be used singly or in combination of two or more. Theamount of the surfactant to be added, with respect to the total mass ofthe polymerizable composition of the present invention, is preferably0.001 mass % to 2.0 mass % and more preferably 0.005 mass % to 1.0 mass%.

(F-7) Other Additives

In addition, the polymerizable composition may contain a co-sensitizerfor the purpose of improving sensitivity of the sensitizing dye and theinitiator to radiation or preventing polymerization inhibition of thephotopolymerizable compound caused by oxygen. A known additive such as adiluent, a plasticizer, or an oil-sensitizing agent may be added asnecessary to improve the physical properties of the cured film.

<Preparation of Dispersion Composition>

Steps for preparing the dispersion composition of the present inventionare not particularly limited. For example, the dispersion composition isprepared by a dispersion process in which the titanium black, being thecolorant (A), the polymer compound (B1), being the dispersant (B), andthe solvent (C) are dispersed with a stirrer, homogenizer, high-pressureemulsifier, wet pulverizer, wet dispersing machine, or the like. Thedispersion process may be performed by two or more dispersion processes(multi-stage dispersion).

<Preparation of Polymerizable Composition>

Steps for preparing the polymerizable composition are not particularlylimited. For example, the polymerizable composition is prepared bymixing the dispersion composition, the polymerizable compound (D), thepolymerization initiator (E), and various types of additives to be usedas desired.

<Light-Shielding Layer>

The light-shielding layer constituting a colored pattern is formed fromthe above-described polymerizable composition. In the colored patternformed from the polymerizable composition, residues are inhibited andflatness is improved. The film thickness of the light-shielding layer 11is not particularly limited. In terms of obtaining the effects of thepresent invention more effectively, the film thickness after drying ispreferably greater than or equal to 0.2 μm and less than or equal to 50μm, more preferably greater than or equal to 0.5 μm and less than orequal to 30 μm, still more preferably greater than or equal to 0.7 μmand less than or equal to 20 μm. A reflectivity (wavelength: 800 nm) ofthe light-shielding layer 11 is preferably 5% or less, more preferably3% or less, and still more preferably 2% or less, and particularlypreferably 1% or less. The surface roughness of the light-shieldinglayer 11 is preferably 0.07 μm or more, more preferably 0.55 μm or more,and particularly preferably greater than or equal to 0.55 μm and lessthan or equal to 1.5 μm. The size of the colored pattern (the length ofone side) is preferably greater than or equal to 0.001 mm and less thanor equal to 5 mm, more preferably greater than or equal to 0.05 mm andless than or equal to 4 mm, and still more preferably greater than orequal to 0.1 mm and less than or equal to 3.5 mm from the viewpoint ofobtaining the effects of the present invention more effectively. Thesurface roughness of the light-shielding layer 11 is measured using astylus profilometer DEKTAK 150 (manufactured by VEECO). The reflectivityof the light-shielding layer 11 was measured using infrared light of 300to 1300 nm incident on the light-shielding layer 11 at an angle ofincidence of 5°, with a spectrometer UV4100 (trade name) manufactured byHITACHI High-Technologies Corporation.

<IR Cut Filter and Method for Manufacturing the Same>

Next, a method for manufacturing the IR cut filter 10 is described. Thelight-shielding layer 11 constitutes a colored portion of the coloredpattern formed from the above-described polymerizable composition. Themethod for manufacturing the IR cut filter 10 described below includes amethod for forming the light-shielding layer 11.

The method for forming the light-shielding layer 11 includes a step(hereinafter may be abbreviated as “polymerizable composition layerforming step”) in which a polymerizable composition layer, being acoating film, is formed by applying a coating liquid, being apolymerizable composition, to the incident surface 6 a of the filterbody 6, a step (hereinafter may be abbreviated as “exposure step”) inwhich the polymerizable composition layer is exposed to light through amask, and a step (hereinafter may be abbreviated as “development step”)in which the polymerizable composition layer after the exposure isdeveloped to form the colored pattern.

To be more specific, the above-described polymerizable composition isapplied to the incident surface 6 a of the filter body 6 directly orthrough another layer to form a polymerizable composition layer (thepolymerizable composition layer forming step), and the polymerizablecomposition layer, being the coating film, is exposed to light through apredetermined mask pattern so that only a portion of the coating filmexposed to light is cured (the exposure step) and then developed with adeveloper (the development step), and thereby a pattern-formed film isformed. Thus, the IR cut filter 10 formed with the light-shielding layer11 is produced.

Hereinafter, referring to FIG. 5, each step in a method formanufacturing the IR cut filter 10 is described.

[Polymerization Composition Layer Forming Step]

In the polymerizable composition layer forming step, as illustrated inparts (a) and (b) of FIG. 5, an above-described polymerizablecomposition 51 is applied to the incident surface 6 a of the filter body6 to form a polymerizable composition layer 52. In this embodiment, thepolymerizable composition layer 52 is formed all over the incidentsurface 6 a, however, the polymerizable composition layer 52 may beformed at least in a region in which the light-shielding layer 11 isformed. A primer coat layer may be provided to the incident surface 6 aof the filter body 6 as necessary for the purpose of improving adhesionwith the polymerizable composition layer 52, preventing diffusion of asubstance, or planarizing the incident surface 6 a.

As for a method for applying the polymerizable composition 51 to theincident surface 6 a, a spray coating method using a spray coater 53 isused in this embodiment and each embodiment described below. Instead ofthe spray coating method, various types of application methods such as aspin coating method, slit coating, an ink jet method, rotation coating,casting coating, roll coating, or a screen printing method may beapplied.

In the case of the spray coating method, the spray coating may beperformed twice or more or four times or more to complete. In the casewhere the spraying is performed twice, the application pressure(atomizing pressure) of the spray or the distance between aspray-discharge section and the filter body 6 may be changed.

The spray coating method can improve the reflectivity of thepolymerizable composition layer 52, however, the adhesion may becomeinsufficient. In the case of the spray coating method, it is consideredthat the size of polymerizable composition particles which constitutethe polymerizable composition layer 52 is controlled by changingapplication conditions. A layer in which the size of the polymerizablecomposition particles is small is formed by the first application (firstcoating), and a layer in which the size of the polymerizable compositionparticles is large is formed by the second application (second coating).Thereby, the adhesion is ensured by the layer in which the size of thepolymerizable composition particles is small. A target reflectivity isachieved by the layer in which the size of the polymerizable compositionparticles is large. In other words, the object of the present inventionis further achieved by a step for forming a layer in which the size ofthe polymerizable composition particles is small, for ensuring theadhesion, and a step for forming a layer (low reflection layer) in whichthe size of the polymerizable composition particles is large, forensuring the low reflectivity. Although the size of the polymerizablecomposition particles is relative, the average particle diameter of thesmall-sized polymerizable composition particles (small particles), whichare formed by spraying the polymerizable composition and drying thepolymerizable composition deposited on an application surface, ispreferably 40 μm or less, and more preferably 20 μm or less. The lowerlimit is in the order of 1 μm. The average particle diameter of thelarge-sized polymerizable composition particles (large particles) ispreferably 50 μm or more, and more preferably 70 μm or more. The upperlimit is in the order of 300 μm. Here, the average particle diameter isobtained from the average value of the particle diameters of 20particles selected arbitrarily while the polymerizable compositionparticles, which are formed by deposition and drying, are observed withan optical microscopic image.

In order to form the small particles, the atomizing pressure of thespray coater 53 is preferably set to 150 kPa or more, more preferably350 kPa or more. The upper limit is in the order of 700 kPa. In order toform the large particles, the atomizing pressure of the spray coater 53is preferably set to 130 kPa or less, more preferably 100 kPa or less.The lower limit is in the order of 50 kPa.

The distance between a discharge section of the polymerizablecomposition 51 in the spray coater 53 and the filter body 6 is increased(distance B) in the case where the layer (the low reflection layer) inwhich the size of the polymerizable composition particles is large isformed, and is decreased (distance S) in the case where the layer inwhich the size of the polymerizable composition particles is small isformed. The distance B is preferably greater than or equal to 1.5 timesthe distance S, more preferably greater than or equal to twice thedistance S, and particularly preferably greater than or equal to threetimes the distance S.

The polymerizable composition applied to the incident surface 6 a isnormally dried at a temperature in a range of 70° C. to 110° C. forapproximately 2 to 4 minutes. Thus, the polymerizable composition layer52 is formed.

Note that a member on which the polymerizable composition layer isformed is not limited to the IR cut filter. The polymerizablecomposition layer may be applied to an optical member (applicationsurface) which requires light-shielding.

[Exposure Step]

In the exposure step, as illustrated in parts (c) and (d) of FIG. 5, thepolymerizable composition layer 52 formed in the polymerizablecomposition layer forming step is exposed to light through a mask 55, sothat only an irradiated portion of the polymerizable composition layer52 is cured. In this embodiment, the mask 55 is formed in a rectangularshape smaller than that of the polymerizable composition layer 52, andplaced over a center portion of the polymerizable composition layer 52(see a part (c) in FIG. 5). The mask 55 covers the polymerizablecomposition layer 52 with the edge portions of the incident surface 6 aof the polymerizable composition layer 52 exposed to the outside. In acase where the polymerizable composition layer 52 is viewed in thenormal direction of the incident surface 6 a, the edge portions areexposed to the outside. An irradiated portion 52 a irradiated with thelight from a light source 56 refers to the exposed edge portions only.The irradiated portion 52 a becomes the light-shielding layer 11.

In this embodiment, a high-pressure mercury lamp is used as the lightsource 56. It is preferred that the exposure is carried out by theirradiation of radiation. As for the radiation used for the exposure,ultraviolet rays such as g rays, h rays, and i rays are preferably used.The high-pressure mercury lamp is more preferred. The irradiationintensity is preferably 5 mJ/cm² to 1500 mJ/cm², more preferably 10mJ/cm² to 1000 mJ/cm², and most preferably 10 mJ/cm² to 800 mJ/cm².

[Development Step]

After the exposure step, an alkali development step (development step)is performed. A non-irradiated portion in the exposure step is elutedinto an alkali aqueous solution. Thereby, as illustrated in a part (e)in FIG. 5, only the irradiated portion 52 a cured by the light remainsand thus the light-shielding layer 11 is formed over the filter body 6.In order to elute the unirradiated portion into the alkali aqueoussolution, a method in which the alkaline aqueous solution is applied tothe polymerizable composition layer 52, a method in which the filterbody 6 formed with the polymerizable composition layer 52 is immersed inthe alkali aqueous solution, or the like may be used. Any method may beused as long as it does not alter or elute the filter body 6 and theirradiated portion 52 a. An organic alkaline aqueous solution ispreferred as the developing solution. The developing temperature isnormally greater than or equal to 20° C. and less than or equal to 30°C. and the developing time is 20 seconds or more and 90 seconds or less.

The alkaline aqueous solution may be, for example, inorganic developerin which alkaline compound such as sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate,or sodium metasilicate is dissolved or an organic alkaline developer inwhich alkaline compound such as aqueous ammonia, ethylamine,diethylamine, dimethylethanolamine, tetramethylammonium hydroxide,tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo-[5,4,0]-7-undecene is dissolved. In the alkaline aqueoussolution, the alkaline compound is dissolved such that the concentrationis 0.001 to 10 mass %, preferably 0.01 to 1 mass %. A water-solubleorganic solvent such as methanol or ethanol, a surfactant, and the likemay be added to the alkaline aqueous solution. Note that in the casewhere the developer composed of the alkaline aqueous solution is used,rinsing with pure water is generally performed after the development.

Note that, in the method for manufacturing the light-shielding layer 11,a curing step in which the formed light-shielding layer 11 is cured byheating and/or exposure may be included as necessary after thepolymerizable composition layer forming step, the exposure step, and thedevelopment step described above. In the case where the light-shieldinglayer 11 is cured with heat, the curing treatment is performed for 5minutes at 200° C. on a hot plate after it is washed with pure water.

Owing to the above-described polymerizable composition, thelight-shielding layer 11 exhibits high adhesion properties with thefilter body 6. The cured polymerizable composition is excellent inresistance to development, so that it is possible to form a patternwhich is excellent in exposure sensitivity and in adhesion with thefilter body 6 of the exposure section and has high-resolution to providea desired cross-sectional shape.

Note that the polymerizable composition layer 52 may be formed by a spincoating method as described above. The spin coating method is a methodfor coating using a spin coater. A spin coater 60, for example, asillustrated in FIG. 6, comprises a mount 62, on which the filter body 6is placed, and a coating die 63. The mount 62 has a mount body 62 a, arotary axis 62 b fixed to the center of the mount body 62 a, and arotary mechanism 62 c. The filter body 6 is placed on the mount body 62a, and the polymerizable composition 51 is supplied onto the filter body6 from the coating die 63 (see a part (a) of FIG. 6). The rotary axis 62b is rotated in a circumferential direction by the rotary mechanism 62 cand thereby the mount body 62 a is rotated together with the rotary axis62 b. Due to this rotation, the supplied polymerizable composition 51spreads over the filter body 6 and thus the polymerizable compositionlayer 52 is formed (see apart (b) in FIG. 6).

Hereinafter, the present invention is described specifically, but thepresent invention is not limited to the following examples as long as itdoes not exceed the scope of the present invention. Note that unlessotherwise specified, “parts” and “%” are in terms of mass. The roomtemperature refers to 25° C.

EXAMPLES Synthesis of Specific Resin 1

600 g of ϵ-caprolactone and 22.8 g of 2-ethyl-1-hexanol were introducedto a three-necked flask 1000 mL, and stirred while nitrogen is blowntherein. 0.1 g of monobutyl tin oxide was added thereto and heated to100° C. 8 hours later, after disappearance of the raw material waschecked by gas chromatography, the mixture was cooled to 80° C. After0.1 g of 2,6-dibutyl-4-methylphenol was added, 27.2 g of2-methacryloyloxyethyl isocyanate was added. After 5-hour stirring, thedisappearance of the raw material was checked by ¹H-NMR, and then themixture was cooled to the room temperature, and thereby 650 g of solidprecursor M1 (the structure below) was obtained. The M1 was identifiedby ¹H-NMR, IR, and mass spectrometry.

80.0 g of the precursor M1, 20.0 g of isobutyl methacrylate, 2.3 g ofdodecyl mercaptan, and 233.3 g of propylene glycol monomethyl etheracetate were introduced in a nitrogen-substituted three-necked flask,and stirred with a stirrer (Three-One Motor manufactured by ShintoScientific Co., Ltd.), and heated up to 75° C. while nitrogen is blowninto the flask. 0.2 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65manufactured by Wako Pure Chemical Industries Co., Ltd.) was addedthereto, and stirred for 2 hours while being heated at 75° C. 2 hourslater, 0.2 g of V-65 was further added. After 3 hours of heating andstirring, a 30% solution of a specific resin 1 described below wasobtained. The ClogP value written beneath a structural unit, on the leftside, of the specific resin 1 represents the ClogP value in a compound(monomer) which corresponds to the structural unit. In the specificresin, the composition ratio in the resin is x=20 and y=80, the numberof atoms in a graft chain excluding hydrogen atoms=257, the acid value=0mgKOH/g, and weight average molecular weight=22000.

Preparation of Titanium Black Dispersion

—Preparation of titanium black A-1 —

100 g of titanium oxide MT-150A (trade name, manufactured by Tayca Co.,Ltd.) with the average particle diameter of 15 nm, 25 g of silicaparticles AEROPERL (registered trademark) 300/30 (manufactured byEvonik) with a BET surface area of 300 m²/g, and 100 g of a dispersantDisperbyk190 (trade name, manufactured by BYK Co., Ltd.) were measuredand mixed together, and 71 g of ion electrochemical exchange water wasadded thereto, and then were subjected to processing for 20 minutesusing the KURABO-made MAZERSTAR KK-400W at revolution speed 1360 rpm androtation speed 1047 rpm. Thereby a uniform mixture aqueous solution wasobtained. A quartz vessel was filled with the aqueous solution andheated to 920° C. in an oxygen atmosphere with a small rotary kiln(manufactured by Motoyama Ltd.), and then the atmosphere was replacedwith nitrogen, and nitride reduction treatment was performed by flowingammonia gas at 100 mL/min for 5 hours at the same temperature. After thecompletion, the recovered powder was ground with a mortar and therebytitanium black A-1 (the dispersoid containing the titanium blackparticles and the Si atoms) in powder form containing the Si atoms andhaving a specific surface area of 73 m²/g was obtained.

The components shown in the following composition 1 are stirred for 15minutes using a stirrer (EUROSTAR manufactured by IKA Co.) to obtain adispersion “a”.

(Composition 1)

The titanium black (A-1) obtained as described above 25 parts 30 mass %solution of propylene glycol monomethyl ether 25 parts acetate, beingthe specific resin 1 Propylene glycol monomethyl ether acetate (PGMEA)(solvent) 50 parts

The obtained dispersion “a” was subjected to a dispersion process underthe following conditions by using Ultra Apex Mill UAM015 manufactured byKotobuki Industries Ltd., and thereby titanium black dispersion wasobtained.

(Dispersion Conditions)

-   Bead diameter: φ 0.05 mm-   Beads filling rate: 75% by volume-   Mill peripheral speed: 8 m/sec-   Volume of mixture liquid to be subjected to dispersion process: 500    g-   Circulation flow rate (pump feed rate): 13 kg/hour-   Temperature of liquid being treated: 25 to 30° C.-   Cooling water: tap water-   Volume of annular chamber of bead mill: 0.15 L-   Number of passes: 90 passes

<Preparation of Polymerizable Composition>

The components of the following composition A were stirred with astirrer to prepare the polymerizable composition.

(Composition A)

Benzyl methacrylate/acrylic acid copolymer 5.0 parts (composition ratio:benzyl methacrylate/acrylic acid copolymer = 80/20 (mass %), weightaverage molecular weight: 25000; binder polymer) Dipentaerythritolhexaacrylate (polymerizable compound) 5.0 parts Ethoxylatedpentaerythritol tetraacrylate (polymerizable 2.0 parts compound)Titanium black dispersion described above 70.0 parts Propylene glycolmonomethyl ether acetate (solvent) 8.94 parts Ethyl 3-ethoxy propionate(solvent) 7.0 parts Polymerization initiator: a compound 1 describedbelow 1.0 part (IRGACURE OXE01 manufactured by BASF) 4-methoxyphenol(polymerization inhibitor) 0.01 parts 3-methacryloxypropyltrimethoxysilane 1.0 part (Silane coupling agent) Megafac F781(manufactured by DIC Ltd.) (surfactant) 0.05 parts

<Formation of Light-Shielding Layer>

The polymerizable composition 51 prepared as described above was appliedover the incident surface 6 a of the filter body 6 by a well-known spraycoating method. Then a heating process (prebaking) was performed for 120seconds by using a hot plate at 100° C. Thereby a polymerizablecomposition layer with the dry film thickness of 1.5 μm was formed.Next, the exposure was performed at the amount of exposure of 1000mJ/cm² with an i-rays stepper exposure device FPA-3000i5+(manufacturedby Canon Ltd.) at the wavelength of 365 nm through an island-patternmask with the 2 μm square pattern size.

Then the filter body 6 formed with the irradiated polymerizablecomposition layer is placed on a horizontal rotary table of a spinshower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.),and puddle development was performed for seconds at 23° C. using 0.3%aqueous solution of tetramethylammonium hydroxide. Thereby theunirradiated portion of the polymerizable composition layer 52 waseluted into the above-mentioned aqueous solution.

Next, the filter body 6 was fixed to the above-mentioned horizontalrotary table by a vacuum chuck system and a rinsing process wasperformed by supplying a shower of pure water through an ejection nozzlefrom the above of the rotation center while the horizontal rotary tablewas rotated by a rotary device at the number of revolution 50 rpm, andthen washed with pure water. After that, the curing treatment wasperformed on a hot plate at 200° C. for 5 minutes. Thus, the IR cutfilter 10 with the incident surface 6 a formed with the light-shieldinglayer 11 was manufactured.

[Example 1] to [Example 3], [Reference Example 1], and [ComparativeExample 1]

The solid-state imaging device 2 illustrated in FIGS. 1 and 2 isinstalled in a digital camera, and then imaging is performed. Thesubject light is incident on the IR cut filter 10 through the takinglens 7. After the IR light is cut by the filter body 6, the subjectlight enters the image sensor 3. At this time, the harmful rays R1, R2,and the like are blocked by the light-shielding layer 11.

In the image sensor 3, the plurality of color pixels arranged in thelight receiving surface photoelectrically convert the incident light andstore the signal charges. At the time of imaging, the signal charge ofeach color pixel is read out sequentially, and three color signals areoutputted. After being subjected to signal processing in an analogProcessing circuit, which has a noise removing circuit and an amplifyingcircuit, incorporated in the digital camera, the three color signals areconverted into image data by an A/D converter. Thus, a taken image isdisplayed.

In an example 1, as illustrated in FIG. 4, L2/L1=1 is satisfied where L1denotes a length from the side end of the filter body 6 to the side endof the image sensor 3 and L2 denotes a length from the side end of thefilter body 6 to the inner end of the light-shielding layer 11. Thepresence or the absence of flare in a taken image and whether theviewing angle is acceptable or unacceptable (rejected) are evaluated. Ascompared with the example 1, in an example 2, L2/L1=0.5 is satisfied. Inan example 3, L2/L1=0.5 is satisfied. In a comparative example,L2/L1=1.2 is satisfied. In the comparative example 1, thelight-shielding layer 11 is not provided. Other conditions were the sameas those in the example 1. The experimental results are shown in FIG. 7.

The experimental result regarding the presence or absence of flare wasevaluated as A in the case where the taken image is free from flare, andevaluated as B in the case where the taken image has little flare, andevaluated as Z in the case where the flare appears notably in takenimage. Note that A and B are the levels which are accepted and Z is thelevel which is rejected.

As a result of the experiments, in the example 1, a clean image freefrom flare was taken and a sufficient viewing angle was obtained. In theexamples 2 and 3, clean images with little flare were taken and theviewing angles were sufficient. Thus, in the examples 1 to 3, thelight-shielding layer 11 blocks the harmful rays such as the reflectivelight R1 and R2 (see FIG. 3). Thereby the incidence of the harmful raysonto the image sensor 3 is inhibited, so that the occurrences of flareand ghost are inhibited.

In a reference example 1, the viewing angle was not as sufficient asthose in the examples 1 to 3. Outer peripheral portions of an image werenot available. However, there was little flare and little ghost. Thereference example 1 had certain effects on the flare and the ghost. Inthe comparative example 1, there was a significant amount of flare. Notethat similar experimental results were obtained after the experimentswere carried out several times with the conditions the same as those inthe examples 1 to 3, the reference example 1, and the comparativeexample 1.

Example 10

The light-shielding layer 11 was formed over the filter body 6 in amanner similar to the example 1. Note that in the example 10, theatomizing pressure of the spray was changed as follows. A layer in whichthe size of the polymerizable composition particles is small was formedfirst (the atomizing pressure was 400 kPa; the average particle diameterof the polymerizable composition particles was 15 μm). Then, a layer inwhich the size of the polymerizable composition particles is large wasformed (the atomizing pressure is 100 kPa; the average particle diameterof the polymerizable composition particles is 80 μm). As a result,little peeling of the light-shielding layer 11 was observed in thecross-cut test, showing excellent adhesion properties of thelight-shielding layer 11.

[Second Embodiment]

In FIG. 8, a solid-state imaging device 20 of a second embodiment isillustrated. Note that the elements which are the same as or similar tothose of the first embodiment are designated with the same referencenumbers and detailed descriptions thereof are omitted.

The solid-state imaging device 20 comprises the image sensor 3, thecircuit board 4, the ceramic plate 5, an IR cut filter 22, the takinglens 7, the lens holder 8, and the support barrel 9. The IR cut filter22 has the filter body 6 and the light shielding layer 21. The lightshielding layer 21 is formed over the entire periphery of the side endfaces of the filter body 6. The light shielding layer 21 is formed to beflush with the incident surface 6 a, and lower portions of the side endfaces of the filter body 6 illustrated in FIG. 8 are not formed with thelight shielding layer 21. In the absence of the light-shielding layer21, the reflective light R3 exited from the taking lens 7 and reflectedby the front surface of the ceramic plate 5 enters the image sensor 3after repetitive reflection and refraction inside the device and therebycauses the flare in a taken image. In this embodiment, however, thelight shielding layer 21 blocks the harmful rays such as the reflectivelight R3 traveling toward the image sensor 3. As a result, a taken imagein which the flare is inhibited is displayed.

Referring to FIG. 9, a method for manufacturing the IR cut filter 22 isdescribed. As illustrated in a part (a) in FIG. 9, the filter body 6 isplaced on the mount 62. The spray coater 53, which is disposed to facethe side face of the mount 62, sprays the polymerizable composition 51onto the side end face of the filter body 6 while the mount 62 isrotated in a circumferential direction with the top face of the mount 62maintained in the horizontal direction. Thus the polymerizablecomposition 51 is applied. After the application, the drying wasperformed under the above-described conditions and thereby apolymerizable composition layer 61 was formed on the side end face ofthe filter body 6 (the polymerizable composition layer forming step).

Next, as illustrated in parts (b) and (c) in FIG. 9, the polymerizablecomposition layer 61 is exposed through a mask 64, so that only aportion of the polymerizable composition layer 61 irradiated with thelight is cured (the exposure step). In this embodiment, the mask 64 hasa rectangular frame form with an opening at the center. The size of theopening is the same as that of the filter body 6 formed with thepolymerizable composition layer 62. The thickness of the mask 64 issmaller than that of the filter body 6. The mask 64 is disposed with itsunderside flush with the exit surface of the filter body 6 asillustrated in FIG. 9. Thus, the mask 64 is provided over the outerperiphery of the polymerizable composition layer 61 (see the part (b) inFIG. 9). The mask 64 covers the polymerizable composition layer 61 suchthat the mask 64 exposes an upper portion of the polymerizablecomposition layer 61 to the outside as illustrated in the drawing. Theedge portion of the polymerizable composition layer 61 is exposed to theoutside when viewed in the normal direction of the incident surface.Only the exposed portion is an irradiated portion 61 a, which isirradiated with the light from the light source 56. The irradiatedportion 61 a becomes the light shielding layer 21.

The exposure (the exposure step) is performed by applying the light fromthe light source 56, which is disposed to face the mount 62, while themount 62 is rotated in a manner similar to that in the polymerizablecomposition layer forming step. After the exposure step, alkalidevelopment step (the development step) is performed. The unirradiatedportion not irradiated in the exposure step is eluted into an alkaliaqueous solution. Thereby, as illustrated in apart (d) of FIG. 9, onlythe irradiated portion 52 a cured by the light remains and thus thelight-shielding layer 21 is formed over the end face of the filter body6. Note that the above-described curing step may be performed after thedevelopment step. Note that, as illustrated in FIG. 10, it is preferredto satisfy L4≤L3 where L3 denotes the length of the filter body 6 in theoptical axis direction and L4 denotes the length from the incidentsurface 6 a of the filter body 6 to a rear end (underside) of the lightshielding layer 21. Thereby the viewing angle in the case of L4≤L3 isgreater than that in the case of L4>L3.

[Example 4] to [Example 6], and [Comparative Example 2]

The solid-state imaging device 20 illustrated in FIG. 8 is installed inthe digital camera, and then imaging is performed. In an example 4, asillustrated in FIG. 10, L4/L3=0.1 was satisfied where L3 denotes thelength of the filter body 6 in the optical axis direction and L4 denotesthe length from the incident surface 6 a of the filter body 6 to therear end of the light shielding layer 21. The presence or absence of theflare in a taken image and whether the viewing angle is accepted orrejected are evaluated. As compared with the example 1, in the example5, L4/L3=0.5 was satisfied. In the example 6, L4/L3=1 was satisfied. Inthe comparative example 2, the light shielding layer 21 was notprovided. Other conditions were the same as those in the example 4. Theexperimental results were shown in FIG. 10. With regard to theexperimental results on the presence or absence of the flare, a level C(acceptable level), which corresponds to a taken image of an acceptablelevel with some flare, was provided in addition to the levels A, B, andZ, which are the same as those in the first embodiment.

As a result of the experiments, in the example 4, an image of anacceptable level with some flare was taken. In examples 5 and 6, cleanimages with little flare were taken. Note that the sufficient viewingangles were obtained in the examples 4 to 6.

In the comparative example 2, a significant amount of flare occurred.Note that similar experimental results were obtained after theexperiments were carried out for several times with the conditions thesame as those in the examples 4 to 6 and the comparative example 2.

[Third Embodiment]

FIG. 12 illustrates a solid-state imaging device 30 of the thirdembodiment. Note that elements which are the same as or similar to thoseof the first embodiment are designated with the same reference numbersand detailed descriptions thereof are omitted.

The solid-state imaging device 30 comprises the image sensor 3, thecircuit board 4, the ceramic plate 5, an IR cut filter 32, the takinglens 7, the lens holder 8, and the support barrel 9. The IR cut filter32 has the filter body 6 and a light-shielding layer 31. Thelight-shielding layer 31 is formed over the entire periphery of the edgeportions and the side end faces of incident surface 6 a of the filterbody 6. In other words, the first and second embodiments are combinedwith each other. In this embodiment, the light-shielding performance ishigher than those of the first and second embodiments, so that theoccurrences of the flare and the ghost are inhibited reliably.

Referring to FIG. 13, a method for manufacturing the IR cut filter 32 isdescribed. As illustrated in a part (a) of FIG. 13, the polymerizablecomposition 51 is applied, with the spray coater 53, to the incidentsurface 6 a and the side end faces of the filter body 6. In order toperform the application to the side end faces of the filter body 6, thefilter body 6 is placed on the rotatable mount 62, and the spray coater53, which is disposed to face the side face of the mount 62, sprays thepolymerizable composition 51 onto the side end faces of the filter body6 while the mount 62 is rotated in a circumferential direction with thetop surface of the mount 62 maintained in the horizontal direction, in amanner similar to that of the second embodiment. After the application,drying is performed under the above-described conditions, and thereby apolymerizable composition layer 71 is formed over the incident surface 6a and the side end faces of the filter body 6 (polymerizable compositionlayer forming step).

Next, as illustrated in parts (b) and (c) of FIG. 13, the exposureprocess is performed with the masks 55 and 64. The exposure is performedby applying the light from the light source 56 disposed above the mount62 and the light source 56 disposed to face the side face of the mount62 while the mount 62 is rotated in a manner similar to that in thepolymerizable composition layer forming step. The alkali developmentstep (the development step) is performed after the exposure step. Theunirradiated portion not irradiated in the exposure step is eluted intoan alkaline aqueous solution. Thereby, as illustrated in a part (d) inFIG. 13, only a portion cured by the light remains, so that thelight-shielding layer 31 is formed over the edge portions and over theside end faces of the incident surface 6 a of the filter body 6. Notethat after the development step, the curing step may be performed asdescribed above.

[Fourth Embodiment]

FIG. 14 illustrates a solid-state imaging device 40 of a fourthembodiment. Note that elements which are the same as or similar to thoseof the third embodiment are designated with the same reference numbersand detailed descriptions thereof are omitted.

The solid-state imaging device 40 comprises the image sensor 3, thecircuit board 4, the ceramic plate 5, an IR cut filter 42, the takinglens 7, the lens holder 8, and the support barrel 9. The IR cut filter42 has the filter body 6 and the light-shielding layer 31. Thelight-shielding layer 31 is formed over the entire periphery of the edgeportions and the side end faces of the incident surface 6 a of thefilter body 6.

A light-shielding layer 41 is formed over an inner wall of the ceramicplate 5. In a case where the light-shielding layer 41 is not formed, thereflective light exited from the taking lens 7 and passed through thefilter body 6 and reflected by the inner wall of the ceramic plate 5 isincident on the image sensor 3, causing the flare in a taken image. Inthis embodiment, however, the light-shielding layer 41 blocks theharmful rays HR from entering the inner wall of the ceramic plate 5. Inthis embodiment, the light-shielding performance is higher than those inthe first to third embodiments, so that the occurrence of the flare isinhibited reliably. In this embodiment, the light-shielding layer 41 isformed by a spray coating method. In a case where a coating is appliedalso to other walls in addition to the inner walls of the ceramic plate5, the light-shielding layer 41 may be formed by the developing processafter the exposure process using a mask (not shown).

Note that, in the above embodiments, the filter body 6 having thereflective film formed on the glass is used, but is not limited thereto.A low-pass filter may be used as the filter body 6.

In the above embodiments, the IR cut filter 10, 22, 32, or 42 is held bythe ceramic plate 5, but the plate is not limited thereto. The IR cutfilter may be held by a resin plate or a metal plate.

What is claimed is:
 1. An IR cut filter disposed and used on a lightreceiving surface side of a solid-state imaging element comprising: afilter body for cutting IR light of subject light traveling toward thelight receiving surface; and a light-shielding layer formed over atleast one of an edge portion of an incident surface of the filter bodyand a side end face of the filter body and blocking visible light,wherein the light-shielding layer is formed over the edge portion of theincident surface of the filter body, and wherein a length L1 from a sideend of the incident surface to a side end of the solid state imagingelement in an orthogonal direction orthogonal to an optical axisdirection and a length L2 from a side end of the filter body to an innerend of the light-sheiding layer in the orthogonal direction satisfyL2≤L1.
 2. The IR cut filter according to claim 1, wherein thelight-shielding layer contains carbon black or titanium black.
 3. The IRcut filter according to claim 1, wherein the light-shielding layer isformed by a spin coating method or a spray coating method.
 4. The IR cutfilter according to claim 1, wherein the light-shielding layer isfurther formed over the side end face, and a length L3 of the filterbody in the optical axis direction and a length L4 from the incidentsurface to a rear end of the light-shielding layer in the optical axisdirection satisfy L4≤L3.
 5. The IR cut filter according to claim 1,wherein a reflectivity of the light-shielding layer at a wavelength of800 nm is 2% or less and surface roughness is 0.55μm or more.
 6. Asolid-state imaging device comprising: a taking lens; a solid-stateimaging element disposed on an exit surface side of the taking lens; anIR cut filter disposed between the taking lens and the solid-stateimaging element, the IR cut filter having a filter body and alight-shielding layer, the filter body cutting IR light of subject lighttraveling toward a light receiving surface of the solid-state imagingelement, the light-shielding layer blocking visible light, thelight-shielding layer being formed over at least one of an edge portionof an incident surface of the filter body and a side end face of thefilter body; and a support plate for supporting the IR cut filter,wherein the light-shielding layer is formed over the edge portion of theincident surface of the filter body, and wherein a length L1 from a sideend of the incident surface to a side end of the solid-state imagingelement in an orthogonal direction orthogonal to an optical axisdirection and a length L2 from a side end of the filter body to an innerend of the light shielding layer in the orthogonal direction satisfyL2≤L1.
 7. An IR cut filter disposed and used on a light receivingsurface side of a solid-state imaging element comprising: a filter bodyfor cutting IR light of subject light traveling toward the lightreceiving surface; and a light-shielding layer formed over a side endface of the filter body and blocking visible light, wherein a length L3of the filter body in an optical axis direction and a length L4 from anincident surface of the filter body to a rear end of the light-shieldinglayer in the optical axis direction satisfy L4≤L3.
 8. The IR cut filteraccording to claim 7, wherein the light-shielding layer contains carbonblack or titanium black.
 9. The IR cut filter according to claim 7,wherein the light-shielding layer is formed by a spin coating method ora spray coating method.
 10. The IR cut filter according to claim 7,wherein a reflectivity of the light-shielding layer at a wavelength of800 nm is 2% or less and surface roughness is 0.55 μm or more.
 11. Asolid-state imaging device comprising: a taking lens; a solid-stateimaging element disposed on an exit surface side of the taking lens; anIR cut filter disposed between the taking lens and the solid-stateimaging element, the IR cut filter having a filter body and alight-shielding layer, the filter body cutting IR light of subject lighttraveling toward a light receiving surface of the solid-state imagingelement, the light-shielding layer blocking visible light, thelight-shielding layer being formed over a side end face of the filterbody; and a support plate for supporting the IR cut filter, wherein alength L3 of the filter body in an optical axis direction and a lengthL4 from an incident surface of the filter body to a rear end of thelight-shielding layer in the optical axis direction satisfy L4≤L3. 12.The IR cut filter according to claim 1, wherein the light-shieldinglayer constitutes a colored pattern and the length of one side of thecolored pattern is in a range from 0.001 to 5 mm.
 13. The IR cut filteraccording to claim 1, wherein the light-shielding layer includes blackcolorant and a polymer compound containing a structural unit having agraft chain and a hydrophobic structural unit that is different from thestructural unit having the graft chain.
 14. The IR cut filter accordingto claim 1, wherein the side end of the filter body is located outsidethe side end of the solid-state imaging element.